Modified aluminum oxy compound, polymerization catalyst and process for producing olefin polymer and alkenyl

ABSTRACT

A modified aluminum oxy compound (A) obtained by reacting an aluminum oxy compound (a), water (b) and a compound having a hydroxyl group (c); a polymerization catalyst component comprising the modified aluminum oxy compound; a polymerization catalyst obtained by contacting said modified aluminum oxy compound (A), a transition metal compound (B) and optionally an organoaluminum compound (C) and a specified boron compound; and a process for producing an olefin polymer or an alkenyl aromatic hydrocarbon polymer with the polymerization catalyst.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a divisional application of U.S. application Ser.No. 09/661,626, filed Sep. 13, 2000 now U.S. Pat. No. 6,664,208 B1,which, in turn, is a continuation-in-part of U.S. application Ser. No.09/391,005, filed Sep. 7, 1999, now abandoned; this application is alsoa continuation-in-part of U.S. application Ser. No. 09/391,662, filesSep. 7, 1999, now abandoned; claiming priority of Japanese ApplicationNos. 10-255287, filed Sep. 9, 1998, 11-254632, filed Sep. 8, 1999 and12-061764, filed Mar. 7, 2000, the entire disclosures of which areincorporated herein by reference in their entireties.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a modified aluminum oxy compound, apolymerization catalyst containing said modified aluminum oxy compoundas a component, and a process for producing a polymer with saidcatalyst.

2. Description of the Related Arts

Many processes for producing an olefin polymer with a polymerizationcatalyst using a transition metal compound (for example, a metalloceneand non-metallocene compound) and an aluminum oxy compound, arewell-known. For example, a process using bis(cyclopentadienyl)zirconiumdichloride and methylaluminoxane, is reported in JP58/019309A. However,in order to obtain the olefin polymer at a high yield, it is necessaryto add a large amount of the aluminum oxy compound such as 1000 to 10000moles of aluminum atom per 1 mole of transition metal atom. This haslead to major problems such as a high production cost and the residue ofa large amount of aluminum atoms in the olefin polymer causes a badinfluence on the properties of the olefin polymer.

In order to solve these problems, many reports concerning the reductionof the amount of aluminum oxy compound used have been made. For example,processes using a transition metal compound and a combination of analuminum oxy compound and an organoaluminum compound are reported inJP60260602A and JP60130604A. Further, a process using methylaluminoxaneand an aluminum oxy compound in which at least one isobutyl group isbonded with an aluminum atom, and a metallocene complex, and the like,are reported in JP63130601A. However, these processes do not reach asufficient solution of the above-mentioned problems.

Further, polymers obtained with these catalysts have a low molecularweight in general, and the improvement has been further required forpractical use.

A process using an aluminum oxy compound having an electron withdrawinggroup or an electron withdrawing group-containing group as an olefinpolymerization catalyst component is recently reported in JP06329714A.According to this process, a highly active catalyst can be obtained, andan olefin polymer with a relatively high molecular weight can beobtained by polymerizing an olefin using said catalyst. However, thecatalyst activity and the molecular weight of the olefin polymerobtained are not always sufficient, the invention of an aluminum oxycompound for realizing the more improvement of activity and themolecular weight of a polymer has been desired in order to produce anindustrially useful olefin polymer.

Moreover, various investigations for synthesis of an α-olefin polymerhaving stereoregularity using a metallocene complex have been furthercarried out, and a trial of synthesizing a highly stereoregular α-olefinpolymer by designing the structure of a metallocene complex is carriedout.

For example, a production example of a highly stereoregular isotacticpropylene polymer using a metallocene complex in which a methyl group isintroduced at 2-position of the indenyl group of a silicon-bridging typebis(indenyl)complex and an isopropyl group, a phenyl group or a naphthylgroup is introduced at 4-position (Organometallics 1994, 13, 954.), anda production example of a highly stereoregular isotactic propylenepolymer using a metallocene complex in which two of mono- totri-substituted η⁵-cyclopentadienyl groups are bridged (JP-B-258725,JP-B-2627669 and JP-B-2668732) are known.

Further, it is reported that a syndiotactic propylene polymer isobtained by using an aluminum oxy compound withisopropylidene(cyclopentadienyl)(fluorenyl)zirconium dichloride which isa metallocene complex having Cs symmetry, or the like (J. Am. Chem.Soc., 1988, 110, 6255.).

SUMMARY OF THE INVENTION

An object of the present invention is to provide a modified aluminum oxycompound that is useful as a component of an olefin polymerizationcatalyst, which catalyst is capable of producing a high molecular weightolefin polymer with a high efficiency, and is prepared by contacting atransition metal compound with the modified aluminum compound.

Another object of the present invention is to provide a highly activeolefin polymerization catalyst component using said aluminum oxycompound.

Further, another object of the present invention is to provide a processfor producing a high molecular weight olefin polymer with saidpolymerization catalyst.

Still further, another object of the present invention is to provide analkenyl aromatic hydrocarbon copolymer of high molecular weight and aprocess for producing the same with said polymerization catalyst.

Moreover, another object of the present invention is to provide acatalyst for α-olefin polymerization capable of producing a highlystereoregular α-olefin polymer, and a process for producing a highlystereoregular α-olefin polymer with said catalyst.

Other objects and advantages of the present invention will be apparentfrom the following description.

Namely, the present invention relates to a modified aluminum oxycompound, which has been modified with a compound having a hydroxygroup, in which the ratio [M2/M1] of the intensity (M2) at 30 ppm to theintensity (M1) at 10 ppm of the spectrum in the ²⁷Al-solid NMR is 0.60or more; a polymerization catalyst component containing (A) saidmodified aluminum oxy compound; and an olefin polymerization catalystobtained by a process that comprises contacting (A) said modifiedaluminum oxy compound, (B) a transition metal compound, and optionally(C) an organoaluminum compound or optionally (C) an organoaluminumcompound and (D) a boron compound. Further, the present inventionrelates to a process for producing an olefin polymer which compriseshomopolymerizing an olefin or copolymerizing olefins with saidpolymerization catalyst, and a process for producing an alkenyl aromatichydrocarbon polymer which comprises homopolymerizing an alkenyl aromatichydrocarbon or copolymerizing an alkenyl aromatic hydrocarbon and anolefin with said polymerization catalyst, and a copolymer of an alkenylaromatic hydrocarbon and an olefin, having a number average molecularweight of 700,000 or more and a molecular weight distribution in termsof a ratio of weight average molecular weight (Mw) to number averagemolecular weight (Mn) [Mw/Mn] of 1.85 to 2.5.

Further, the present invention relates to a catalyst for α-olefinpolymerization obtained by contacting said modified aluminum oxycompound with (B) a transition metal compound having a capability ofstereoregular polymerization of α-olefin. Further, the present inventionrelates to a process for producing a stereoregular α-olefin polymerusing said catalyst.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows an ²⁷Al-solid NMR spectrum of a sample obtained by dryingMMAO3A (toluene solution, manufactured by TOSOH-AKZO Co., Ltd.) used asin Example 1, under reduced pressure. The ratio of H2 to H1 was 0.27from this spectrum.

FIG. 2 shows an ²⁷Al-solid NMR spectrum of a sample obtained by drying areaction product obtained by mixing MMAO3A (toluene solution,manufactured by TOSOH-AKZO Co., Ltd.) and water with stirring as inExample 1, under reduced pressure. The ratio of L2 to L1 was 0.75 fromthis spectrum.

FIG. 3 shows an ²⁷Al-solid NMR spectrum of a sample obtained by drying areaction product obtained by mixing MMAO3A (toluene solution,manufactured by TOSOH-AKZO Co., Ltd.) and water with stirring and thenadding pentafluorophenol thereto with stirring as in Example 1, underreduced pressure. The ratio of M2 to M1 was 1.26 from this spectrum.

FIG. 4 shows an ²⁷Al-solid NMR spectrum of a sample obtained by drying areaction product obtained by mixing MMAO3A (toluene solution,manufactured by TOSOH-AKZO Co., Ltd.) and pentafluorophenol withstirring as in Example 1, under reduced pressure. The ratio of N2 to N1was 0.57 from this spectrum.

FIG. 5 shows an ²⁷Al-solid NMR spectrum of a sample obtained by drying areaction product obtained by mixing MMAO3A (toluene solution,manufactured by TOSOH-AKZO Co., Ltd.) and pentafluorophenol withstirring and then adding water with stirring as in Example 2, underreduced pressure. The ratio of M2 to M1 was 0.70 from this spectrum.

FIG. 6 shows an ²⁷Al-solid NMR spectrum of a sample obtained by drying areaction product obtained by simultaneously mixing MMAO3A (manufacturedby TOSOH-AKZO Co., Ltd.), water and pentafluorophenol with stirring asin Example 25, under reduced pressure. The ratio of M2 to M1 was 1.04from this spectrum. H1, H2, L1, L2, M1, M2, N1 and N2 are as definedbelow.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is illustrated in detail below.

(A) Modified Aluminum Oxy Compound

The modified aluminum oxy compound (A) of the present invention is amodified aluminum oxy compound in which an aluminum oxy compound ismodified with a compound having a hydroxy group, and in which the ratio[M2/M1] of the intensity (M2) at 30 ppm to the intensity (M1) at 10 ppmof the spectrum in the ²⁷Al-solid NMR is 0.60 or more. Herein, the solidNMR spectrum means a NMR spectrum obtained by measuring a solid sampleat a magic angle spinning using a high speed rotation In the presentinvention, the ²⁷Al-solid NMR spectrum measurement of the modifiedaluminum oxy compound or an aluminum oxy compound is conducted asfollows:

When the modified aluminum oxy compound or aluminum oxy compoundobtained is in a solution state dissolved in a solvent, the solvent isremoved by a known method such as a reduced-pressure drying, etc. to dryand solidify the modified aluminum oxy compound or aluminum oxycompound. Herein-after, the modified aluminum oxy compound or aluminumoxy compound dried and solidified is sometimes referred to as “solid NMRmeasurement sample”.

In a nitrogen box or a globe box, the solid NMR measurement sample waspacked in a rotation cell(,or a spinner or a rotor) for solid NMRmeasurement in an appropriate amount so that the cell can be stablyrotated A solid NMR spectrum at a magnetic field intensity of 7.0 T (¹Hobservation magnetic field intensity at 300 MHz) is measured using asolid NMR spectrometer in which the cell is capable of high speedrotating with a nitrogen gas or an inert gas. The sample is measuredunder a cell rotation speed of 8 kHz or more, preferably 12 to 15 kHz.As the standard of the chemical shift, the peak appeared in highmagnetic field side of an active alumina is determined as 7 ppm. Thewidth of the spectrum is set to 400 ppm or more, preferably 600 to 1000ppm as a chemical shift width of ²⁷Al, considering that the group ofpeaks to be measured can be measured. The pulse width is set to smallerthan the 90° pulse width used in a solution ²⁷Al-NMR spectrum. The pulseinterval is determined so that the relaxation does not occur.

As a measurement pulse sequences, there is illustrated a single pulsemethod without decoupling, for example, a pulse sequence is a HPDECwithout decoupling. The measurement is usually carried out room attemperature (about 20 to about 25° C.). In the case of solid NMRmeasurement of ²⁷Al nucleus, shapes of peaks and the chemical shiftdepend on magnetic field intensity due to an interaction of secondaryquadrupole of nucleus.

Due to the reason as above, for comparisons of spectra measured, it isnecessary that measurements of ²⁷Al-solid NMR of various solid NMRsamples are carried out at the same magnetic field intensity.

After the measurement, the data are subjected to Fourier transfer toobtain an ²⁷Al-solid NMR spectrum. In the obtained ²⁷Al-solid NMRspectrum, the phase and baseline correction thereof are compensated sothat the heights of bases of the highest magnetic field peak group andthe lowest magnetic field peak group among peak groups appeared from avicinity of −150 ppm to a vicinity of 150 ppm, are mutually made thesame height, and the spectrum of a part in which no peak is observed inregions −150 ppm under and 150 ppm over, become parallel to the chemicalshift axis (axis of abscissa) as far as possible. The baseline as astandard is drawn between bases of the highest magnetic field peak groupand the lowest magnetic field peak group. A vertical line is drawn at 10ppm to the chemical shift axis (axis of abscissa), The intensity M1 isdefined as a distance between the intersecting point of the verticalline with baseline and the intersecting point of the vertical line withthe spectrum. And, when a vertical is drawn at 30 ppm to the chemicalshift axis (axis of abscissa), the intensity M2 is defined as a distancebetween the intersecting point of the vertical line with the baselineand the intersecting point of the vertical line with the spectrum.Further, H1 and H2, L1 and L2, and N1 and N2 (these are as definedbelow) can be determined by the same method as above.

The modified aluminum oxy compound of the present invention has a ratioof M2/M1 calculated from these values above of 0.60 or more, preferably0.65 or more, most preferably 0.70 to 1.5. The modified aluminum oxycompound of the present invention satisfies the scope of M2/M1 describedabove, and is one modified with a compound having a hydroxy group. Themodified aluminum oxy compound of the present invention is obtained byreacting an aluminum oxy compound (a) having a ratio of an intensity(H2) at 30 ppm to a intensity (H1) at 10 ppm of less than 0.35, water(b) and a compound (c) having a hydroxy group.

The present invention will be described in more detail.

(a) Aluminum Oxy Compound

As the aluminum oxy compound used as a raw material of the modifiedaluminum oxy compound of the present invention, there is illustrated analuminum oxy compound having a ratio of the intensity (H2) at 30 ppm tothe intensity (H1) at 10 ppm, in the ²⁷Al-solid NMR spectrum, of lessthan 0.35.

As (a) aluminum oxy compound used in the present invention, an aluminumoxy compound soluble in an aromatic hydrocarbon or an aliphatichydrocarbon which represented by the general formula (1) or (2)described below, is preferable.

(wherein each of the R groups respectively indicates a hydrocarbon grouphaving 1 to 20 carbon atoms, which R groups may be the same ordifferent, and m represents a number of 1 to 50.)

The hydrocarbon group in the above-mentioned general formula (1) or (2)includes an alkyl group, alkenyl group, aryl group and aralkyl grouphaving up to 20 carbon atoms, and the like, and an alkyl group having 1to 20 carbon atoms is preferable.

The specific examples thereof include methylaluminoxane,ethylaluminoxane, propylaluminoxane, butylaluminoxane,isobutylaluminoxane, methylethylaluminoxane, methylbutylaluminoxane,methylisobutylaluminoxane, and the like are exemplified. Most of thesecompounds are commercially available or can be synthesized by well-knownmethods. Among them, methylisobutyl aluminoxane is preferable inparticular, R in the above-mentioned general formula (1) or (2)represents a methyl group or an isobutyl group in respective cases. Analuminum oxy compound in which the existence ratio of a methyl group asR to an isobutyl group as R (methyl group/isobutyl group) is (5 to95)/(95 to 5) is more preferable, and the ratio is preferably (10 to90)/(90 to 10) in particular.

These aluminum oxy compounds may be used alone or in combination of 2 ormore kinds.

(b) Water

When the modified aluminum oxy compound of the present invention isproduced, a water (b) is used. The water (b) is preferably a distilledwater or de-ionized water. When water (b) is used in the presentinvention, it is unknown in detail why the molecular weight of thealuminum oxy compound seems to increase, and the viscosity thereofincreases, and as the case may be, the precipitation of a solid, areobserved.

(c) Compound Having Hydroxyl Group

The compound (c) having a hydroxyl group used in preparation of themodified aluminum oxy compound (A) of the present invention, is acompound having at least one hydroxyl group in its molecule, and anorganic compound having a hydroxyl group is preferable. An alcoholcompound, a phenol compound or a silanol compound is more preferable.Herein, the alcohol compound preferably includes a compound indicated bythe general formula below:CR¹R²R³—OH(wherein each of R¹, R² and R³ independently represents a hydrogen atomor a hydrocarbon group having 1 to 20 carbon atoms, and they may bemutually the same or different.)

The hydrocarbon group in the above-mentioned general formula includes analkyl group, an aralkyl group, an aryl group and the like, and thesegroups may be optionally substituted with a halogen atom.

Tertiary alcohols and alcohols substituted with a halogen atom arepreferable, and in particular, tert-butyl alcohol, triphenylmethanol,tricyclohexylmethanol or 1,1,1,3,3,3-hexafluoroisopropanol ispreferable.

Further, as the phenol compound, non-substituted phenols or substitutedphenols can be used. Wherein the substituent includes a halogen atom, analkyl group, aralkyl group, aryl group, silyl group, alkoxy group,aralkyloxy group, aryloxy group or silyloxy group which may besubstituted with a halogen atom, or the like.

Specific examples of such phenol compound include 2-substituted phenolssuch as 2-methylphenol, 2-ethylphenol, 2-n-butylphenol,2-isobutylphenol, 2-tert-butylphenol, 2-n-propylphenol,2-isopropylphenol, 2-phenylphenol, 2-fluorophenol, 2-chlorophenol,2-bromophenol and the like; 3-substituted phenols such as3-methylphenol, 3-ethylphenol, 3-n-butylphenol, 3-isobutylphenol,3-tert-butylphenol, 3-n-propylphenol, 3-isopropylphenol, 3-phenylphenol,3-fluorophenol, 3-chlorophenol, 3-bromophenol and the like;4-substituted phenols such as 4-methylphenol, 4-ethylphenol,4-n-butylphenol, 4-isobutylphenol, 4-tert-butylphenol, 4-n-propylphenol,4-isopropylphenol, 4-phenylphenol, 4-fluorophenol, 4-chlorophenol,4-bromophenol and the like; 2,6-substituted phenols such as2,6-dimethylphenol, 2,6-diethylphenol, 2,6-di-n-butylphenol,2,6-diisobutylphenol, 2,6-di-tert-butylphenol, 2,6-di-n-propylphenol,2,6-diisopropylphenol, 2,6-diphenylphenol, 2,6-difluorophenol,2,6-dichlorophenol, 2,6-dibromophenol and the like; 2,6,X-substitutedphenols (X is one or more numerals selected from 3, 4 and 5) such as2,4,6-trimethylphenol, 2,6-di-tert-butyl-4-methylphenol,2,3,5,6-tetrafluorophenol, pentafluorophenol and the like;2,3-substituted phenols such as 2,3-difluorophenol and the like;2,4-substituted phenols such as 2,4-difluorophenol and the like;3,5-substituted phenols such as 3,5-dimethylphenol, 3,5-diethylphenol,3,5-di-n-butylphenol, 3,5-diisobutylphenol, 3,5-di-tert-butylphenol,3,5-di-n-propylphenol, 3,5-diisopropylphenol, 3,5-diphenylphenol,3,5-difluorophenol, 3,5-dichlorophenol, 3,5-dibromophenol and the like;phenols having 2 or more hydroxy groups such as catechol, resorcinol,hydroquinone, bisphenol-A, 2,2-thiobis-6-tert-butyl-4-methylphenol andthe like.

As the phenol compound, a phenol having bulky substituents at2,6-position or a halogenated phenol is preferable, and in particular,pentafluorophenol is preferable.

Further, the silanol is preferably a compound represented by the generalformula below:SiR⁴R⁵R⁶—OH(wherein each of R⁴, R⁵ and R⁶ dependently represents a hydrogen atom ora hydrocarbon group having 1 to 20 carbon atoms, they may be mutuallythe same or different.)

The hydrocarbon group in the above-mentioned general formula includes analkyl group, an aralkyl group, an aryl group and the like, and thesegroups may be optionally substituted with a halogen atom.

A tertiary silanol or a silanol substituted with a halogen atom ispreferred, and triphenylsilanol or tricyclohexylsilanol is morepreferred.

As the compound (c) having a hydroxyl group used in the presentinvention, an alcohol compound or a phenol compound is preferable, andin particular, pentafluorophenol, triphenylmethanol,tricyclohexylmethanol or 1,1,1,3,3,3-hexafluoroisopropanol ispreferable.

These compounds having a hydroxyl group may be used alone or incombination of 2 or more kinds.

(d) Preparation of Modified Aluminum Oxy compound (A)

The modified aluminum oxy compound (A) of the present invention isobtained by reacting (a) an aluminum oxy compound having a ratio of theintensity (H2) at 30 ppm in the ²⁷Al-solid NMR spectrum to the intensity(H1) at 10 ppm in that of less than 0.35, (b) water and (c) a compoundhaving a hydroxyl group.

The reaction is preferably carried out in an inert gas atmosphere. Thereaction temperature is not specifically limited, but is usually −80° C.to 200° C. and preferably −50° C. to 120° C. The reaction time isusually 1 minute to 12 hours and preferably 2 minutes to 1 hour.Further, in this reaction, a solvent may be used, and these reactants(a), (b) and (c) may be directly reacted without a solvent. The solventused is not specifically limited, and includes an aliphatic hydrocarbonsolvent or an aromatic hydrocarbon solvent. Specific example thereofincludes hexane, heptane, benzene, toluene or the like.

The modified aluminum oxy compound of the present invention ispreferably obtained by reacting (a) the aluminum oxy compound with (b)water to obtain (a′) an aluminum oxy compound having a ratio (L2/L1) ofan intensity(L2) at 30 ppm in an ²⁷Al-solid NMR spectrum to anintensity(L1) at 10 ppm in that of 0.35 or more, and then reacting (a′)the resulting aluminum oxy compound with (c) a compound having ahydroxyl group, or by reacting (a)the aluminum oxy compound with (c) thecompound having a hydroxyl group to obtain (a″) an aluminum oxy compoundhaving a ratio(N2/N1) of an intensity(N2) at 30 ppm in a ²⁷Al-solid NMRspectrum to an intensity (N1) at 10 ppm in that of 0.35 or more, andthen reacting (a″) with (b) water. When the (a′) the aluminum oxycompound is available, a modified aluminum oxy compound (A) is obtainedby reacting the (a′) with (c) a compound having a hydroxyl group.

The ratio, L2/L1 is preferably 0.35 or more and less than 0.90, morepreferably 0.35 to 0.85.

And, the ratio of (L2/L1) to (H2/H1) [(L2/L1)/(H2/H1)] is preferably 1.5or more, more preferably 1.5 or more and less than 9.0. Further, theratio, N2/N1 is preferably 0.35 or more and less than 0.65, morepreferably 0.35 to 0.60.

The molar ratio of respective components used in the reaction is notspecifically limited, and the molar ratio of the component (a) (in termsof mol of Al atom) to the component (b) ((a)/(b)) is preferably withinthe range of 1/3 to 1/0.01, more preferably 1/1 to 1/0.05. Further, themolar ratio of the component (a) (in terms of mol of Al atom) to thecomponent (c) is preferably within the range of 1/3 to 1/0.01, morepreferably 1/1 to 1/0.05. The molar ratio of the component (a′) (interms of mol of Al atom) to the component (c) ((a′)/(c)) is preferablywithin the range of 1/3 to 1/0.01, more preferably 1/1 to 1/0.05.Further, the molar ratio of the component (a″) (in terms of mol of Alatom) to the component (b) is preferably within the range of 1/3 to1/0.01, more preferably 1/1 to 1/0.05.

The modified aluminum oxy compound of the present invention obtained bythe preparation method described above or the like can be used as apolymerization catalyst component after purification by isolation suchas recrystallization or the like, but the reaction solution containingthe modified aluminum oxy compound can be also used as thepolymerization catalyst component as it is.

The modified aluminum oxy compound of the present invention is useful asthe polymerization catalyst component. Examples of the polymerizationcatalyst using the modified aluminum oxy compound of the presentinvention include the polymerization catalyst obtained by contacting (A)the modified aluminum oxy compound and (B) a transition metal compound;the polymerization catalyst obtained by contacting (A) the modifiedaluminum oxy compound, (B) the transition metal compound and (C) theorganoaluminum compound; and the polymerization catalyst obtained bycontacting (A) the modified aluminum oxy compound, (B) the transitionmetal compound, (C) the organoaluminum compound and (D) any one boroncompounds (D1) to (D3) described below:

(D1) a boron compound represented by the general formula BQ¹Q²Q³,

(D2) a boron compound represented by the general formula G⁺(BQ¹Q²Q³Q⁴)⁻,and

(D3) a boron compound represented by the general formula(L—H)⁺(BQ¹Q²Q³Q⁴)⁻ (wherein B represents a boron atom in the trivalentvalence state; Q¹ to Q⁴ may be the same or different and represent ahalogen atom, a hydrocarbon group, a halogenated hydrocarbon group, asubstituted silyl group, an alkoxy group or a di-substituted aminogroup; G⁺ represents an inorganic or organic cation; L represents aneutral Lewis base; and (L—H)⁺ represents a Brfnsted acid).

The polymerization catalyst of the present invention will be describedin more detail below.

(B) Transition Metal Compound

The transition metal compound used for the olefin polymerizationcatalyst of the present invention is not specifically limited so far asit is a transition metal compound having an olefin polymerizationactivity. A transition metal compound having a transition metal atom ofthe Group IV to X of the Periodic Table of the Elements and LanthanideSeries is preferable. Example of the transition metal compound includesa transition metal compound indicated by the general formula (3)described below, a μ-oxo type transition metal compound obtained byreacting the transition metal compound with water as a dimer thereof,and the like.L_(a)MX_(b)  (3)(wherein M is a transition metal atom of the Group IV to Group X of thePeriodic Table or Lanthanide Series; L is a group having acyclopentadienyl type anion skeleton or a group containing ahetero-atom, and a plurality of L groups may be optionally linked indirect, or through a group containing a carbon atom, a silicone atom, anitrogen atom, an oxygen atom, a sulfur atom or a phosphorus atom; X isa halogen atom or a hydrocarbon group having 1 to 20 carbon atoms; arepresents a numeral satisfying an equation of 0<a≦8; b represents anumeral satisfying an equation of 0<b≦8; and a and b are properlyselected so that the transition metal compound become neutral takinginto account of the valency of the transition metal M and the valenciesof L and X.)

In the general formula (3) representing the transition metal compound, Mis a transition metal atom of the Group IV to Group X of the PeriodicTable (IUPAC 1985) or Lanthanide Series. Specific examples of thetransition metal atom include titanium, zirconium, hafnium, vanadium,niobium, tantalum, chromium, iron, ruthenium, cobalt, rhodium, nickel,palladium, samarium, ytterbium and the like.

In the general formula (3) representing the transition metal compound, Lis a group having a cyclopentadienyl type anion skeleton or a groupcontaining a hetero-atom, and L groups may be the same or different.Further, L groups may be optionally linked in direct, or through a groupcontaining a carbon atom, a silicone atom, a nitrogen atom, an oxygenatom, a sulfur atom or a phosphorus atom.

A cyclopentadienyl type anion skeleton in L includes a cyclopentadienylgroup, a substituted cyclopentadienyl group, an indenyl group, asubstituted indenyl group, a fluorenyl group, a substituted fluorenylgroup and the like. Examples of the group having a cyclopentadiene typeanion skeleton include an η⁵-(substituted)cyclopentadienyl group, anη⁵-(substituted)indenyl group, an η⁵-(substituted)fluorenyl group andthe like. Specific examples include an η⁵-cyclopentadienyl group, anη⁵-methylcyclopentadienyl group, an η⁵-tert-butylcyclopentadienyl group,an η⁵-1,2-dimethylcyclopentadienyl group, anη⁵-1,3-dimethylcyclopentadienyl group, anη⁵-1-tert-butyl-2-methylcyclopentadienyl group, anη⁵-1-tert-butyl-3-methylcyclopentadienyl group, anη⁵-1-methyl-2-isopropylcyclopentadienyl group, anη⁵-1-methyl-3-isopropylcyclopentadienyl group, anη⁵-1,2,3-trimethylcyclopentadienyl group, anη⁵-1,2,4-trimethylcyclopentadienyl group, anη⁵-tetramethylcyclopentadienyl group, an η⁵-pentamethylcyclopentadienylgroup, an η⁵-indenyl group, an η⁵-4,5,6,7-tetrahydroindenyl group, anη⁵-2-methylindenyl group, an η⁵-3-methylindenyl group, anη⁵-4-methylindenyl group, an η⁵-5-methylindenyl group, anη⁵-6-methylindenyl group, an η⁵-7-methylindenyl group, anη⁵-2-tert-butylindenyl group, an η⁵-3-tert-butylindenyl group, anη⁵-4-tert-butylindenyl group, an η⁵-5-tert-butylindenyl group, anη⁵-6-tert-butylindenyl group, an η⁵-7-tert-butylindenyl group, anη⁵-2,3-dimethylindenyl group, an η⁵-4,7-dimethylindenyl group, anη⁵-2,4,7-trimethylindenyl group, an η⁵-2-methyl-4-isopropylindenylgroup, an η⁵-4,5-benzindenyl group, an η⁵-2-methyl-4,5-benzindenylgroup, an η⁵-4-phenylindenyl group, an η⁵-2-methyl-5-phenylindenylgroup, an η⁵-2-methyl-4-phenylindenyl group, anη⁵-2-methyl-4-naphthylindenyl group, an η⁵-fluorenyl group, anη⁵-2,7-dimethylfluorenyl group, an η⁵-2,7-di-tert-butylfluorenyl group(herein-after, η⁵ may be omitted for simplifying), and substitutionproducts thereof, etc.

The hetero-atom in the group containing a hetero-atom includes an oxygenatom, a sulfur atom, a nitrogen atom, a phosphorus atom and the like,and examples thereof include an alkoxy group, an aryloxy group, athioalkoxy group, a thioaryloxy group, an alkylamino group, an arylaminogroup, an alkylphosphino group, an arylphosphino group, or an aromaticor aliphatic heterocyclic group having an oxygen atom, a sulfur atom, anitrogen atom and/or a phosphorus atom, a chelating ligand.

Specific examples of the group containing a hetero-atom include amethoxy group, an ethoxy group, a n- or iso-propoxy group, a n-, sec-,iso- or tert-butoxy group, a phenoxy group, a 2-methylphenoxy group, a2,6-dimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a2-ethylphenoxy group, a 4-n-propylphenoxy group, a 2-isopropylphenoxygroup, a 2,6-diisopropylphenoxy group, a 4-sec-butylphenoxy group, a4-tert-butylphenoxy group, a 2,6-di-sec-butylphenoxy group, a4-tert-butyl-4-methylphenoxy group, a 2,6-di-tert-butylphenoxy group, a4-methoxyphenoxy group, a 2,6-dimethoxyphenoxy group, a3,5-dimethoxyphenoxy group, a 2-chlorophenoxy group, a 4-nitrosophenoxygroup, a 4-nitrophenoxy group, a 2-aminophenoxy group, a 3-aminophenoxygroup, a 4-aminothiophenoxy group, a 2,3,6-trichlorophenoxy group, a2,4,6-trifluorophenoxy group, a thiomethoxy group, a dimethylaminogroup, a diethylamino group, a di-n- or iso-propylamino group, adiphenylamino group, an isopropylamino group, a tert-butylamino group, apyrrolyl group, a dimethylphosphino group, a 2-(2-oxy-1-propyl)phenoxygroup, catechol, resorcinol, 4-isopropylcatechol, 3-methoxycatechol, a1,8-dihydroxynahpthyl group, a 1,2-dihydroxynahpthyl group, a2,2′-biphenyldiol group, a 1,1′-bi-2-naphthol group, a2,2′-dihydroxy-6,6′-dimethylbiphenyl group, a4,4′,6,6′-tetra-tert-butyl-2,2′-methylenediphenoxy group, a4,4′,6,6′-tetramethyl-2,2′-isobutylidenediphenoxy group and the like.

Further, the chelating ligand means a ligand having a plural number ofcoordinating positions, and specific examples include acetylacetonate,diimine, oxazoline, bisoxazoline, terpyridine, acylhydrazone,diethylenetriamine, triethylenetetramine, porphyrin, a crown ether, acryptate and the like.

The mutual groups having the cyclopentadienyl type anion skeleton, thegroup having a cyclopentadienyl type anion skeleton and the groupcontaining a hetero-atom, or the mutual groups containing a hetero-atommay be directly linked, or may be linked through a group containing acarbon atom, a silicone atom, a nitrogen atom, an oxygen atom, a sulfuratom or a phosphorus atom, respectively. Examples of the group includealkylene groups such as an ethylene group, a propylene group and thelike, substituted alkylene groups such as a dimethylmethylene group, adiphenylmethylene group and the like, or a silylene group, substitutedsilylene groups such as a dimethylsilylene group, a diphenylsilylenegroup, a tetramethyldisilylene group and the like, or hetero-atoms suchas a nitrogen atom, an oxygen atom, a sulfur atom and/or a phosphorusatom and the like, etc.

X in the general formula (3) representing the transition metal compoundis a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.Specific examples of X include a fluorine atom, a chlorine atom, abromine atom, an iodine atom, and examples of the hydrocarbon grouphaving 1 to 20 carbon atoms include alkyl groups, aryl groups, aralkylgroups (e.g. a methyl group, an ethyl group, a n-propyl group, anisopropyl group, a n-butyl group, a phenyl group, a benzyl group), andthe like.

Among the transition metal compound, specific examples of the compoundin which a transition metal is a titanium atom includebis(cyclopentadienyl)titanium dichloride,bis(methylcyclopentadienyl)titanium dichloride,bis(n-butylcyclopentadienyl)titanium dichloride,bis(dimethylcyclopentadienyl)titanium dichloride,bis(ethylmethylcyclopentadienyl)titanium dichloride,bis(trimethylcyclopentadienyl)titanium dichloride,bis(tetramethylcyclopentadienyl)titanium dichloride,bis(pentamethylcyclopentadienyl)titanium dichloride,bis(indenyl)titanium dichloride, bis(4,5,6,7-tetrahydroindenyl)titaniumdichloride, bis(fluorenyl)titanium dichloride,cyclopentadienyl(pentamethylcyclopentadienyl)titanium dichloride,cyclopentadienyl(indenyl)titanium dichloride,cyclopentadienyl(fluorenyl)titanium dichloride,indenyl(fluorenyl)titanium dichloride,pentamethylcyclopentadienyl(indenyl)titanium dichloride,pentamethylcyclopentadienyl(fluorenyl)titanium dichloride,ethylenebis(cyclopentadienyl)titanium dichloride,ethylenebis(2-methylcyclopentadienyl)titanium dichloride,ethylenebis(3-methylcyclopentadienyl)titanium dichloride,ethylenebis(2-n-butylcyclopentadienyl)titanium dichloride,ethylenebis(3-n-butylcyclopentadienyl)titanium dichloride,ethylenebis(2,3-dimethylcyclopentadienyl)titanium dichloride,ethylenebis(2,4-dimethylcyclopentadienyl)titanium dichloride,ethylenebis(2,5-dimethylcyclopentadienyl)titanium dichloride,ethylenebis(3,4-dimethylcyclopentadienyl)titanium dichloride,ethylenebis(2,3-ethylmethylcyclopentadienyl)titanium dichloride,ethylenebis(2,4-ethylmethylcyclopentadienyl)titanium dichloride,ethylenebis(2,5-ethylmethylcyclopentadienyl)titanium dichloride,ethylenebis(3,5-ethylmethylcyclopentadienyl)titanium dichloride,ethylenebis(2,3,4-trimethylcyclopentadienyl)titanium dichloride,ethylenebis(2,3,5-trimethylcyclopentadienyl)titanium dichloride,ethylenebis(tetramethylcyclopentadienyl)titanium dichloride,ethylenebis(indenyl)titanium dichloride,ethylenebis(4,5,6,7-tetrahydroindenyl)titanium dichloride,ethylenebis(2-phenylindenyl)titanium dichloride,ethylenebis(2-methylindenyl)titanium dichloride,ethylenebis(2-methyl-4-phenylindenyl)titanium dichloride,ethylenebis(2-methyl-4-naphthylindenyl)titanium dichloride,ethylenebis(2-methyl-4,5-benzoindenyl)titanium dichloride,ethylenebis(fluorenyl)titanium dichloride,ethylene(cyclopentadienyl)(pentamethylcyclopentadienyl)titaniumdichloride, ethylene(cyclopentadienyl)(indenyl)titanium dichloride,ethylene(methylcyclopentadienyl)(indenyl)titanium dichloride,ethylene(n-butylcyclopentadienyl)(indenyl)titanium dichloride,ethylene(tetramethylcyclopentadienyl)(indenyl)titanium dichloride,ethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,ethylene(methylcyclopentadienyl)(fluorenyl)titanium dichloride, ethylene(pentamethylcyclopentadienyl)(fluorenyl)titanium dichloride,ethylene(n-butylcyclopentadienyl)(fluorenyl)titanium dichloride,ethylene(tetramethylpentadienyl)(fluorenyl)titanium dichloride,ethylene(indenyl)(fluorenyl)titanium dichloride,isopropylidenebis(cyclopentadienyl)titanium dichloride,isopropylidenebis(2-methylcyclopentadienyl)titanium dichloride,isopropylidenebis(3-methylcyclopentadienyl)titanium dichloride,isopropylidenebis(2-n-butylcyclopentadienyl)titanium dichloride,isopropylidenebis(3-n-butylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,3-dimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,4-dimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,5-dimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(3,4-dimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,3-ethylmethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,4-ethylmethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,5-ethylmethylcyclopentadienyl)titanium dichloride,isopropylidenebis(3,5-ethylmethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,3,4-trimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,3,5-trimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(tetramethylcyclopentadienyl)titanium dichloride,isopropylidenebis(indenyl)titanium dichloride,isopropylidenebis(4,5,6,7-tetrahydroindenyl)titanium dichloride,isopropylidenebis(2-phenylindenyl)titanium dichloride,isopropylidenebis(2-methylindenyl)titanium dichloride,isopropylidenebis(2-methyl-4-phenylindenyl)titanium dichloride,isopropylidenebis(2-methyl-4-naphthylindenyl)titanium dichloride,isopropylidenebis(2-methyl-4,5-benzoindenyl)titanium dichloride,isopropylidenebis(fluorenyl)titanium dichloride,isopropylidene(cyclopentadienyl)(tetramethylcyclopentadienyl)titaniumdichloride, isopropylidene(cyclopentadienyl)(indenyl)titaniumdichloride, isopropylidene(methylcyclopentadienyl)(indenyl)titaniumdichloride, isopropylidene(n-butylcyclopentadienyl)(indenyl)titaniumdichloride, isopropylidene(tetramethylcyclopentadienyl)(indenyl)titaniumdichloride, isopropylidene(cyclopentadienyl)(fluorenyl)titaniumdichloride, isopropylidene(methylcyclopentadienyl)(fluorenyl)titaniumdichloride, isopropylidene(n-butylcyclopentadienyl)(fluorenyl)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(fluorenyl)titaniumdichloride, isopropylidene (indenyl)(fluorenyl)titanium dichloride,

dimethylsilylenebis(cyclopentadienyl)titanium dichloride,dimethylsilylenebis(2-methylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(3-methylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2-n-butylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(3-n-butylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,3-dimethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,4-dimethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,5-dimethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(3,4-dimethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,3-ethylmethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,4-ethylmethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,5-ethylmethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(3,5-ethylmethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,3,4-trimethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(2,3,5-trimethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(tetramethylcyclopentadienyl)titanium dichloride,dimethylsilylenebis(indenyl)titanium dichloride,dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)titanium dichloride,dimethylsilylenebis(2-methylindenyl)titanium dichloride,dimethylsilylenebis(2-methyl-4-phenylindenyl)titanium dichloride,dimethylsilylenebis(2-methyl-4-naphthylindenyl)titanium dichloride,dimethylsilylenebis(2-methyl-4,5-benzoindenyl)titanium dichloride,dimethylsilylene(cyclopentadienyl)(indenyl)titanium dichloride,dimethylsilylene(methylcyclopentadienyl)(indenyl)titanium dichloride,dimethylsilylene(n-butylcyclopentadienyl)(indenyl)titanium dichloride,dimethylsilylene(tetramethylcyclopentadienyl)(indenyl)titaniumdichloride, dimethylsilylene(cyclopentadienyl)(fluorenyl)titaniumdichloride, dimethylsilylene(methylcyclopentadienyl)(fluorenyl)titaniumdichloride, dimethylsilylene(n-butylcyclopentadienyl)(fluorenyl)titaniumdichloride,dimethylsilylene-(tetramethylcyclopentadienyl)(indenyl)titaniumdichloride, dimethylsilylene-(indenyl)(fluorenyl)titanium dichloride,

cyclopentadienyltitanium trichloride,pentamethylcyclopentadienyltitanium trichloride,cyclopentadienyl(dimethylamido)titanium dichloride,cyclopentadienyl(phenoxy)titanium dichloride,cyclopentadienyl(2,6-dimethylphenyl)titanium dichloride,cyclopentadienyl(2,6-diisopropylphenyl)titanium dichloride,cyclopentadienyl(2,6-di-tert-butylphenyl)titanium dichloride,pentamethylcyclopentadienyl(2,6-dimethylphenyl)titanium dichloride,pentamethylcyclopentadienyl(2,6-diisopropylphenyl)titanium dichloride,pentamethylcyclopentadienyl(2,6-di-tert-butylphenyl)titanium dichloride,indenyl(2,6-diisopropylphenyl)titanium dichloride,fluorenyl(2,6-diisopropylphenyl)titanium dichloride,methylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,methylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titanium dichloride,methylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, methylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, methylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride, methylene(fluorenyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, methylene(fluorenyl)(3-phenyl-2-phenoxy)titanium dichloride,methylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,methylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, isopropylidene(cyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, isopropylidene(fluorenyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride, isopropylidene(fluorenyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, isopropylidene(fluorenyl)(3-phenyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,isopropylidene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, diphenylmethylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride, diphenylmethylene(fluorenyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, diphenylmethylene(fluorenyl)(3-phenyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-trimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,diphenylmethylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, dimethylsilylene(cyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(cyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilylene(methylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(methylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilylene(n-butylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(n-butylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(tert-butylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-dimethyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride,dimethylsilylene(trimethylsilylcyclopentadienyl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilylene(indenyl)(2-phenoxy)titanium dichloride,dimethylsilylene(indenyl)(3-methyl-2-phenoxy)titanium dichloride,dimethylsilylene(indenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,dimethylsilylene(indenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,dimethylsilylene(indenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(indenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, dimethylsilylene(indenyl)(3,5-diamyl-2-phenoxy)titaniumdichloride, dimethylsilylene(fluorenyl)(2-phenoxy)titanium dichloride,dimethylsilylene(fluorenyl)(3-methyl-2-phenoxy)titanium dichloride,dimethylsilylene(fluorenyl)(3,5-dimethyl-2-phenoxy)titanium dichloride,dimethylsilylene(fluorenyl)(3-tert-butyl-2-phenoxy)titanium dichloride,dimethylsilylene(fluorenyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(3,5-di-tert-butyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(5-methyl-3-phenyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(3-tert-butyldimethylsilyl-5-methyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(5-methyl-3-trimethylsilyl-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(3-tert-butyl-5-methoxy-2-phenoxy)titaniumdichloride,dimethylsilylene(fluorenyl)(3-tert-butyl-5-chloro-2-phenoxy)titaniumdichloride, dimethylsilylene(fluorenyl)(3,5-diamyl-2-phenoxy)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(1-naphthox-2-yl)titaniumdichloride and the like, and compounds wherein (2-phenoxy) of thesecompounds is replaces with (3-phenyl-2-phenoxy),(3-trimethylsilyl-2-phenoxy) or (3-tert-butyldimethylsilyl-2-phenoxy),compounds wherein dimethylsilylene of these compounds is replaced withdiethylsilylene, diphenylsilylene or dimethoxysilylene, compoundswherein dichloride of these compounds is replaced with difluoride,dibromide, diiodide, dimethyl, diethyl, diisopropyl, bis(dimethylamido),bis(diethylamido), dimethoxide, diethoxide, di-n-butoxide ordiisopropoxide.

(tert-butylamido)tetramethylcyclopentadienyl-1,2-ethanediyltitaniumdichloride,(tert-butylamido)tetramethylcyclopentadienyl-1,2-ethanediyltitaniumdimethyl,(tert-butylamido)tetramethylcyclopentadienyl-1,2-ethanediyltitaniumdibenzyl,(methylamido)tetramethylcyclopentadienyl-1,2-ethanediyltitaniumdichloride,(ethylamido)tetramethylcyclopentadienyl-1,2-ethanediyltitaniumdichloride,(tert-butylamido)tetramethylcyclopentadienyldimethylsilanetitaniumdichloride,(tert-butylamido)tetramethylcyclopentadienyldimethylsilanetitaniumdimethyl,(tert-butylamido)tetramethylcyclopentadienyldimethylsilane-titaniumdibenzyl, (benzylamido)tetramethylcyclopentadienyldimethylsilanetitaniumdichloride,(phenylphosphido)tetramethylcyclopentadienyldimethyl-silanetitaniumdibenzyl, (tert-butylamido)indenyl-1,2-ethanediyltitanium dichloride,(tert-butylamido)indenyl-1,2-ethanediyltitanium dimethyl,(tert-butylamido)tetrahydroindenyl-1,2-ethanediyltitanium dichloride,(tert-butylamido)tetrahydroindenyl-1,2-ethanediyltitanium dimethyl,(tert-butylamido)fluorenyl-1,2-ethanediyltitanium dichloride,(tert-butylamido)fluorenyl-1,2-ethanediyltitanium dimethyl,(tert-butylamido)indenyldimethylsilanetitanium dichloride,(tert-butylamido)indenyldimethylsilanetitanium dimethyl,(tert-butylamido)tetrahydroindenyldimethylsilanetitanium dichloride,(tert-butylamido)tetrahydroindenyldimethylsilanetitanium dimethyl,(tert-butylamido)fluorenyldimethylsilanetitanium dichloride,(tert-butylamido)fluorenyldimethylsilanetitanium dimethyl,(dimethylaminomethyl)tetramethylcyclopentadienyltitanium(III)dichloride, (dimethylaminoethyl)tetramethylcyclopentadienyltitanium(III)dichloride,(dimethylaminopropyl)tetramethylcyclopentadienyltitanium(III)dichloride, (N-pyrrolidinylethyl)tetramethylcyclopentadienyltitaniumdichloride, (B-dimethylaminoborabenzene)cyclopentadienylzirconiumdichloride, cyclopentadienyl(9-mesitylboraanthracenyl)zirconiumdichloride, 2,2′-thiobis[4-methyl-6-(1-methylethyl)phenoxy]titaniumdichloride, 2,2′-thiobis[4,6-dimethylphenoxy]titanium dichloride,2,2′-thiobis(4-methyl-6-tert-butylphenoxy)titanium dichloride,2,2′-methylenebis(4-methyl-6-tert-butylphenoxy)titanium dichloride,2,2′-ethylenebis(4-methyl-6-tert-butylphenoxy)titanium dichloride,2,2′-sulfinylbis(4-methyl-6-tert-butylphenoxy)titanium dichloride,2,2′-(4,4′,6,6′-tetra-tert-butyl-1,1′-biphenoxy)titanium dichloride,2,2′-thiobis[4-methyl-6-tert-butylphenoxy]titanium diisopropoxide,2,2′-methylenebis(4-methyl-6-tert-butylphenoxy)titanium diisopropoxide,2,2′-ethylenebis(4-methyl-6-tert-butylphenoxy)titanium diisopropoxide,2,2′-sulfinylbis(4-methyl-6-tert-butylphenoxy)titanium diisopropoxide,(di-tert-butyl-1,3-propanediamido)titanium dichloride,(dicyclohexyl-1,3-propanediamido)titanium dichloride,[bis(trimethylsilyl)-1,3-propanediamido]titanium dichloride,[bis(tert-butyldimethylsilyl)-1,3-propanediamido]titanium dichloride,[bis(2,6-dimethylphenyl)-1,3-propanediamido]titanium dichloride,[bis(2,6-diisopropylphenyl)-1,3-propanediamido]titanium dichloride,[bis(2,6-di-tert-butylphenyl)-1,3-propanediamido]titanium dichloride,[bis(triisopropylsilyl)naphthalenediamido]titanium dichloride,[bis(trimethylsilyl)naphthalenediamido]titanium dichloride,[bis(tert-butyldimethylsilyl)naphthalenediamido]titanium dichloride,[bis(tert-butyldimethylsilyl)naphthalenediamido]titanium dibromide,[hydrotris(3,5-dimethylpyrazolyl)borate]titanium trichloride,[hydrotris(3,5-dimethylpyrazolyl)borate]titanium tribromide,[hydrotris(3,5-dimethylpyrazolyl)borate]titanium triiodide,[hydrotris(3,5-diethylpyrazolyl)borate]titanium trichloride,[hydrotris(3,5-diethylpyrazolyl)borate]titanium tribromide,[hydrotris(3,5-diethylpyrazolyl)borate]titanium triiodide,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]titanium trichloride,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]titanium tribromide,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]titanium triiodide,[tris(3,5-dimethylpyrazolyl)methyl]titanium trichloride,[tris(3,5-dimethylpyrazolyl)methyl]titanium tribromide,[tris(3,5-dimethylpyrazolyl)methyl]titanium triiodide,[tris(3,5-diethylpyrazolyl)methyl]titanium trichloride,[tris(3,5-diethylpyrazolyl)methyl]titanium tribromide,[tris(3,5-diethylpyrazolyl)methyl]titanium triiodide,[tris(3,5-di-tert-butylpyrazolyl)methyl]titanium trichloride,[tris(3,5-di-tert-butylpyrazolyl)methyl]titanium tribromide,[tris(3,5-di-tert-butylpyrazolyl)methyl]titanium triiodide,μ-oxobis{isopropylidene(cyclopentadienyl)(2-phenoxy)titanium chloride},μ-oxobis{isopropylidene(cyclopentadienyl)(2-phenoxy)titanium methoxide},μ-oxobis{isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumchloride},μ-oxobis{isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniummethoxide},μ-oxobis{isopropylidene(methylcyclopentadienyl)(2-phenoxy)titaniumchloride},μ-oxobis{isopropylidene(methylcyclopentadienyl)(2-phenoxy)titaniummethoxide},μ-oxobis{isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumchloride},μ-oxobis{isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniummethoxide},μ-oxobis{isopropylidene(tetramethylcyclopentadienyl)(2-phenoxy)titaniumchloride},μ-oxobis{isopropylidene(tetramethylcyclopentadienyl)(2-phenoxy)titaniummethoxide},μ-oxobis{isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumchloride},μ-oxobis{isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniummethoxide},μ-oxobis{dimethylsilylene(cyclopentadienyl)(2-phenoxy)titaniumchloride},μ-oxobis{dimethylsilylene(cyclopentadienyl)(2-phenoxy)titaniummethoxide},μ-oxobis{dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumchloride},μ-oxobis{dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniummethoxide},μ-oxobis{dimethylsilylene(methylcyclopentadienyl)(2-phenoxy)titaniumchloride},μ-oxobis{dimethylsilylene(methylcyclopentadienyl)(2-phenoxy)titaniummethoxide},μ-oxobis{dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumchloride},μ-oxobis{dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniummethoxide},μ-oxobis{dimethylsilylene(tetramethylcyclopentadienyl)(2-phenoxy)titaniumchloride},μ-oxobis{dimethylsilylene(tetramethylcyclopentadienyl)(2-phenoxy)titaniummethoxide},α-oxobis{dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumchloride},μ-oxobis{dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniummethoxide}di-μ-oxobis[isopropylidene(cyclopentadienyl)(2-phenoxy)titanium],di-μ-oxobis[isopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium],di-μ-oxobis[isopropylidene(methylcyclopentadienyl)(2-phenoxy)titanium],di-μ-oxobis[isopropylidene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium],di-μ-oxobis[isopropylidene(tetramethylcyclopentadienyl)(2-phenoxy)titanium],di-μ-oxobis[isopropylidene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium],di-μ-oxobis[dimethylsilylene(cyclopentadienyl)(2-phenoxy)titanium],di-μ-oxobis[dimethylsilylene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium],di-μ-oxobis[dimethylsilylene(methylcyclopentadienyl)(2-phenoxy)titanium],di-μ-oxobis[dimethylsilylene(methylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium],di-μ-oxobis[dimethylsilylene(tetramethylcyclopentadienyl)(2-phenoxy)titanium],di-μ-oxobis[dimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titanium]and the like.

Further, compounds wherein a titanium atom is replaced with a zirconiumatom or a hafnium atom can be similarly exemplified in theabove-mentioned titanium compounds. Among the transition metalcompounds, specific examples of a compound in which a transition metalatom is a vanadium atom include vanadium acetylacetonate, vanadiumtetrachloride, vanadium oxy trichloride and the like.

Among the transition metal compounds, specific examples of a compound inwhich a transition metal atom is a samarium atom includebis(pentamethylcyclopentadienyl)samarium methyltetrahydrofuran and thelike.

Among the transition metal compounds, specific examples of a compound inwhich a transition metal atom is an ytterbium atom includebis(pentamethylcyclopentadienyl)ytterbium methyltetrahydrofuran and thelike.

Among the transition metal compounds, specific examples of a compound inwhich a transition metal atom is a nickel atom include2,2′-methylenebis[(4R)-4-phenyl-5,5′-dimethyloxazoline]nickeldichloride,2,2′-methylenebis[(4R)-4-phenyl-5,5′-dimethyloxazoline]nickel dibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5′-diethyloxazoline]nickel dichloride,2,2′-methylenebis[(4R)-4-phenyl-5,5′-diethyloxazoline]nickel dibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5′-di-n-propyloxazoline]nickeldichloride,2,2′-methylenebis[(4R)-4-phenyl-5,5′-di-n-propyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5′-diisopropyloxazoline]nickeldichloride,2,2′-methylenebis[(4R)-4-phenyl-5,5′-diisopropyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5′-dicyclohexyloxazoline]nickeldichloride,2,2′-methylenebis[(4R)-4-phenyl-5,5′-dicyclohexyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5′-dimethoxyoxazoline]nickeldichloride,2,2′-methylenebis[(4R)-4-phenyl-5,5′-dimethoxyoxazoline]nickeldibromide, 2,2′-methylenebis[(4R)-4-phenyl-5,5′-diethoxyoxazoline]nickeldichloride,2,2′-methylenebis[(4R)-4-phenyl-5,5′-diethoxyoxazoline]nickel dibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5′-diphenyloxazoline]nickeldichloride,2,2′-methylenebis[(4R)-4-phenyl-5,5′-diphenyloxazoline]nickel dibromide,methylenebis[(4R)-4-methyl-5,5′-di-(2-methylphenyl)oxazoline]nickeldibromide,methylenebis[(4R)-4-methyl-5,5′-di-(3-methylphenyl)oxazoline]nickeldibromide,methylenebis[(4R)-4-methyl-5,5′-di-(4-methylphenyl)oxazoline]nickeldibromide,methylenebis[(4R)-4-methyl-5,5′-di-(2-methoxyphenyl)oxazoline]nickeldibromide,methylenebis[(4R)-4-methyl-5,5′-di-(3-methoxyphenyl)oxazoline]nickeldibromide,methylenebis[(4R)-4-methyl-5,5′-di-(4-methoxyphenyl)oxazoline]nickeldibromide,methylenebis[spiro{(4R)-4-methyloxazoline-5,1′-cyclobutane}]nickeldibromide,methylenebis[spiro{(4R)-4-methyloxazoline-5,1′-cyclopentane}]nickeldibromide,methylenebis[spiro{(4R)-4-methyloxazoline-5,1′-cyclohexane}]nickeldibromide,methylenebis[spiro{(4R)-4-methyloxazoline-5,1′-cycloheptane)}]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-dimethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-diethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-n-propyloxazoline]nickeldibromide, methylenebis[(4R)-4-isopropyl-5,5-diisopropyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-dicyclohexyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-diphenyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-(2-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-(3-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-(4-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-(2-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-(3-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isopropyl-5,5-di-(4-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isopropyloxazoline-5,1′-cyclobutane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isopropyloxazoline-5,1′-cyclopentane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isopropyloxazoline-5,1′-cyclohexane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isopropyloxazoline-5,1′-cycloheptane}]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-dimethyloxazoline]nickeldibromide, 2,2′-methylenebis[(4R)-4-isobutyl-5,5-diethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-n-propyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-diisopropyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-dicyclohexyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-diphenyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-(2-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-(3-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-(4-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-(2-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-(3-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-isobutyl-5,5-di-(4-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isobutyloxazoline-5,1′-cyclobutane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isobutyloxazoline-5,1′-cyclopentane)}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isobutyloxazoline-5,1′-cyclohexane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-isobutyloxazoline-5,1′-cycloheptane)}]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-dimethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-diethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-n-propyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-diisopropyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-diphenyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-dicyclohexyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-(2-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-(3-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-(4-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-(2-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-(3-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-tert-butyl-5,5-di-(4-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-tert-butyloxazoline-5,1′-cyclobutane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-tert-butyloxazoline-5,1′-cyclopentane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-tert-butyloxazoline-5,1′-cyclohexane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-tert-butyloxazoline-5,1′-cycloheptane}]nickeldibromide, 2,2′-methylenebis[(4R)-4-phenyl-5,5-dimethyloxazoline]nickeldibromide, 2,2′-methylenebis[(4R)-4-phenyl-5,5-diethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-n-propyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-diisopropyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-dicyclohexyloxazoline]nickeldibromide, 2,2′-methylenebis[(4R)-4-phenyl-5,5-diphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-(2-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-(3-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-(4-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-(2-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-(3-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-phenyl-5,5-di-(4-methoxyphenyl)oxazoline]nickeldibromide,methylenebis[spiro{(4R)-4-phenyloxazoline-5,1′-cyclobutane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-phenyloxazoline-5,1′-cyclopentane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-phenyloxazoline-5,1′-cyclohexane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-phenyloxazoline-5,1′-cycloheptane}]nickeldibromide, 2,2′-methylenebis[(4R)-4-benzyl-5,5-dimethyloxazoline]nickeldibromide, 2,2′-methylenebis[(4R)-4-benzyl-5,5-diethyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-di-n-propyloxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-diisopropyloxazoline]nickeldibromide, 2,2′-methylenebis[(4R)-4-benzyl-5,5-dicyclohexyloxazoline]nickel dibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-diphenyl)oxazoline]nickel dibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-di-(2-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-di-(3-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-di-(4-methylphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-di-(2-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-di-(3-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[(4R)-4-benzyl-5,5-di-(4-methoxyphenyl)oxazoline]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-benzyloxazoline-5,1′-cyclobutane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-benzyloxazoline-5,1′-cyclopentane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-benzyloxazoline-5,1′-cyclohexane}]nickeldibromide,2,2′-methylenebis[spiro{(4R)-4-benzyloxazoline-5,1′-cycloheptane}]nickeldibromide, and compounds in which (4R) in each of the above-mentionedcompounds corresponds to (4S), etc. Further, examples of the meso typeisomer include compounds in which (4R) of two skeletons in each of thecompounds which are mentioned above as the optically active substancesof bisoxazolines were changed to (4R) of one oxazoline skeleton and (4S)of another oxazoline skeleton, and[hydrotris(3,5-dimethylpyrazolyl)borate]nickel chloride,[hydrotris(3,5-dimethylpyrazolyl)borate]nickel bromide,[hydrotris(3,5-dimethylpyrazolyl)borate]nickel iodide,[hydrotris(3,5-dimethylpyrazolyl)borate]nickel methyl,[hydrotris(3,5-dimethylpyrazolyl)borate]nickel ethyl,[hydrotris(3,5-dimethylpyrazolyl)borate]nickel allyl,[hydrotris(3,5-dimethylpyrazolyl)borate]nickel methallyl,[hydrotris(3,5-diethylpyrazolyl)borate]nickel chloride,[hydrotris(3,5-diethylpyrazolyl)borate]nickel bromide,[hydrotris(3,5-diethylpyrazolyl)borate]nickel iodide,[hydrotris(3,5-diethylpyrazolyl)borate]nickel methyl,[hydrotris(3,5-diethylpyrazolyl)borate]nickel ethyl,[hydrotris(3,5-diethylpyrazolyl)borate]nickel allyl,[hydrotris(3,5-diethylpyrazolyl)borate]nickel methallyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel chloride,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel bromide,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel iodide,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel methyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel ethyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel allyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]nickel methallyl, compoundsindicated by the structural formula described below:

(wherein each of R⁷ and R⁸ is a 2,6-diisopropylphenyl group, and X, R⁹and R¹⁰ are any one of the combination of the substituents representedin Table 1 described below.) R⁹ and R¹⁰ may be one bi-valent group (e.g.a acenaphthyl group) in one united body.

TABLE 1 R⁹ = R¹⁰ = H R⁹ = R¹⁰ = methyl Acenaphthyl by R⁹ & R¹⁰ X = F X =F X = F R⁹ = R¹⁰ = H R⁹ = R¹⁰ = methyl Acenaphthyl by R⁹ & R¹⁰ X = Cl X= Cl X = Cl R⁹ = R¹⁰ = H R⁹ = R¹⁰ = methyl Acenaphthyl by R⁹ & R¹⁰ X = IX = I X = I R⁹ = R¹⁰ = H R⁹ = R¹⁰ = methyl Acenaphthyl by R⁹ & R¹⁰ X =Methyl X = methyl X = methyl R⁹ = R¹⁰ = H R⁹ = R¹⁰ = methyl Acenaphthylby R⁹ & R¹⁰ X = Ethyl X = ethyl X = ethyl R⁹ = R¹⁰ = H R⁹ = R¹⁰ = methylAcenaphthyl by R⁹ & R¹⁰ X = n-propyl X = n-propyl X = n-propyl R⁹ = R¹⁰= H R⁹ = R¹⁰ = methyl Acenaphthyl by R⁹ & R¹⁰ X = isopropyl X =isopropyl X = isopropyl R⁹ = R¹⁰ = H R⁹ = R¹⁰ = methyl Acenaphthyl by R⁹& R¹⁰ X = n-butyl X = n-butyl X = n-butyl R⁹ = R¹⁰ = H R⁹ = R¹⁰ = methylAcenaphthyl by R⁹ & R¹⁰ X = phenyl X = phenyl X = phenyl R⁹ = R¹⁰ = H R⁹= R¹⁰ = methyl Acenaphthyl by R⁹ & R¹⁰ X = benzyl X = benzyl X = benzyl

Further, compounds wherein a nickel atom is replaced with a palladiumatom, a cobalt atom, a rhodium atom or a ruthenium atom can be similarlyexemplified in the above-mentioned nickel compounds.

Among the transition metal compounds, specific examples of a compound inwhich a transition metal atom is an iron atom include2,6-bis-[1-(2,6-dimethylphenylimino)ethyl]pyridineiron dichloride,2,6-bis-[1-(2,6-diisopropylphenylimino)ethyl]pyridineiron dichloride,2,6-bis-[1-(2-tert-butylphenylimino)ethyl]pyridineiron dichloride,[hydrotris(3,5-dimethylpyrazolyl)borate]iron chloride,[hydrotris(3,5-dimethylpyrazolyl)borate]iron bromide,[hydrotris(3,5-dimethylpyrazolyl)borate]iron iodide,[hydrotris(3,5-dimethylpyrazolyl)borate]iron methyl,[hydrotris(3,5-dimethylpyrazolyl)borate]iron ethyl,[hydrotris(3,5-dimethylpyrazolyl)borate]iron allyl,[hydrotris(3,5-dimethylpyrazolyl)borate]iron methallyl,[hydrotris(3,5-diethylpyrazolyl)borate]iron chloride,[hydrotris(3,5-diethylpyrazolyl)borate]iron bromide,[hydrotris(3,5-diethylpyrazolyl)borate]iron iodide,[hydrotris(3,5-diethylpyrazolyl)borate]iron methyl,[hydrotris(3,5-diethylpyrazolyl)borate]iron ethyl,[hydrotris(3,5-diethylpyrazolyl)borate]iron allyl,[hydrotris(3,5-diethylpyrazolyl)borate]iron methallyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron chloride,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron bromide,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron iodide,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron methyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron ethyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron allyl,[hydrotris(3,5-di-tert-butylpyrazolyl)borate]iron methallyl, and thelike.

Further, compounds wherein an iron atom is replaced with a cobalt atomor a nickel atom can be similarly exemplified in the above-mentionediron compounds.

These transition metal compounds may be used alone, or in combination of2 or more kinds of the compounds.

Moreover, the catalyst for α-olefin polymerization obtained bycontacting the above-mentioned modified aluminum oxy compound with atransition metal compound having a capability of stereoregularpolymerization of an α-olefin is illustrated.

The transition metal compound used for the catalyst for α-olefinpolymerization is not specifically limited if it is a transition metalcompound capable of producing a stereoregular α-olefin polymer such asan isotactic propylene polymer or a syndiotactic propylene polymer, andfor example, can be appropriately selected from the fore-mentionedtransition metal compounds.

Among the transition metal compounds having a capability ofstereoregular polymerization of an α-olefin, specific examples of acompound in which the transition metal atom is a titanium atom includeethylenebis(2-methylcyclopentadienyl)titanium dichloride,ethylenebis(2-n-butylcyclopentadienyl)titanium dichloride,ethylenebis(3-methylcyclopentadienyl)titanium dichloride,ethylenebis(3-n-butylcyclopentadienyl)titanium dichloride,ethylenebis(2,3-dimethylcyclopentadienyl)titanium dichloride,ethylenebis(2,4-dimethylcyclopentadienyl)titanium dichloride,ethylenebis(2-ethyl-3-methylcyclopentadienyl)titanium dichloride,ethylenebis(2-ethyl-4-methylcyclopentadienyl)titanium dichloride,ethylenebis(2-methyl-3-ethylcyclopentadienyl)titanium dichloride,ethylenebis(2-methyl-4-ethylcyclopentadienyl)titanium dichloride,ethylenebis(2,3,4-trimethylcyclopentadienyl)titanium dichloride,ethylenebis(2,4,5-trimethylcyclopentadienyl)titanium dichloride,ethylenebis{2-(2-furyl)-3,5-dimethylcyclopentadienyl}titaniumdichloride,ethylenebis{2-(2-furyl)-4,5-dimethylcyclopentadienyl}titaniumdichloride, ethylenebis(indenyl)titanium dichloride,ethylenebis(4,5,6,7-tetrahydroindenyl)titanium dichloride,ethylenebis(2-phenylindenyl)titanium dichloride,ethylenebis(fluorenyl)titanium dichloride,ethylene(cyclopentadienyl)(fluorenyl)titanium dichloride,ethylene(methylcyclopentadienyl)(fluorenyl)titanium dichloride,ethylene(n-butylcyclopentadienyl)(fluorenyl)titanium dichloride,ethylene(tetramethylpentadienyl)(fluorenyl)titanium dichloride,isopropylidenebis(2-methylcyclopentadienyl)titanium dichloride,isopropylidenebis(2-n-butylcyclopentadienyl)titanium dichloride,isopropylidenebis(3-methylcyclopentadienyl)titanium dichloride,isopropylidenebis(3-n-butylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,3-dimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,4-dimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2-ethyl-3-methylcyclopentadienyl)titanium dichloride,isopropylidenebis(2-ethyl-4-methylcyclopentadienyl)titanium dichloride,isopropylidenebis(2-methyl-3-ethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2-methyl-4-ethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,3,4-trimethylcyclopentadienyl)titanium dichloride,isopropylidenebis(2,4,5-trimethylcyclopentadienyl)titanium dichloride,isopropylidenebis{2-(2-furyl)-3,5-dimethylcyclopentadienyl}titaniumdichloride,isopropylidenebis{2-(2-furyl)-4,5-dimethylcyclopentadienyl}titaniumdichloride, isopropylidenebis(indenyl)titanium dichloride,isopropylidenebis(4,5,6,7-tetrahydroindenyl)titanium dichloride,isopropylidenebis(2-phenylindenyl)titanium dichloride,isopropylidene(cyclopentadienyl)(fluorenyl)titanium dichloride,isopropylidene (methylcyclopentadienyl)(fluorenyl)-titanium dichloride,isopropylidene(n-butylcyclopentadienyl)(fluorenyl)titanium dichloride,isopropylidene(tetramethylcyclopentadienyl)(fluorenyl)titaniumdichloride, dimethylsilylenebis(2-methylcyclopentadienyl)titaniumdichloride, dimethylsilylenebis(2-n-butylcyclopentadienyl)titaniumdichloride, dimethylsilylenebis(3-methylcyclopentadienyl)titaniumdichloride, dimethylsilylenebis(3-n-butylcyclopentadienyl)titaniumdichloride, dimethylsilylenebis(2,3-dimethylcyclopentadienyl)titaniumdichloride, dimethylsilylenebis(2,4-dimethylcyclopentadienyl)titaniumdichloride,dimethylsilylenebis(2-ethyl-3-methylcyclopentadienyl)titaniumdichloride,dimethylsilylenebis(2-ethyl-4-methylcyclopentadienyl)titaniumdichloride,dimethylsilylenebis(2-methyl-3-ethylcyclopentadienyl)titaniumdichloride,dimethylsilylenebis(2-methyl-4-ethylcyclopentadienyl)titaniumdichloride, dimethylsilylenebis(2,3,4-trimethylcyclopentadienyl)titaniumdichloride, dimethylsilylenebis(2,4,5-trimethylcyclopentadienyl)titaniumdichloride,dimethylsilylenebis{2-(2-furyl)-3,5-dimethylcyclopentadienyl}titaniumdichloride,dimethylsilylenebis{2-(2-furyl)-4,5-dimethylcyclopentadienyl}titaniumdichloride, dimethylsilylenebis(indenyl)titanium dichloride,dimethylsilylenebis(2-methyl-indenyl)titanium dichloride,dimethylsilylenebis(2-methyl-4-phenylindenyl)titanium dichloride,dimethylsilylenebis(2-methyl-4,5-benzo-indenyl)titanium dichloride,dimethylsilylenebis(2-methyl-4-naphthylindenyl)titanium dichloride,dimethylsilylenebis(2-methyl-4-isopropyl-1-indenyl)titanium dichloride,dimethylsilylene(2-methyl-1-indenyl)(2-methyl-4-phenyl-1-indenyl)titaniumdichloride,dimethylsilylene(2-methyl-1-indenyl)(2-methyl-4-naphthyl-1-indenyl)titaniumdichloride,dimethylsilylene(2-methyl-1-indenyl)(2-methyl-4-isopropyl-1-indenyl)titaniumdichloride,dimethylsilylene(2-methyl-4-phenyl-1-indenyl)(2-methyl-4-naphthyl-1-indenyl)titaniumdichloride,dimethylsilylene(2-methyl-4-phenyl-1-indenyl)(2-methyl-4-isopropyl-1-indenyl)titaniumdichloride,dimethylsilylene(2-methyl-4-naphthyl-1-indenyl)(2-methyl-4-isopropyl-1-indenyl)titaniumdichloride, dimethylsilylenebis(2-ethyl-indenyl)titanium dichloride,dimethylsilylenebis(2-ethyl-4-phenyl-1-indenyl)titanium dichloride,dimethylsilylenebis(2-ethyl-4,5-benzo-indenyl)titanium dichloride,dimethylsilylenebis(2-ethyl-4-naphthyl-1-indenyl)titanium dichloride,dimethylsilylenebis(2-ethyl-4-isopropyl-1-indenyl)titanium dichloride,dimethylsilylene(2-ethyl-1-indenyl)(2-methyl-4-phenyl-1-indenyl)titaniumdichloride,dimethylsilylene(2-ethyl-1-indenyl)(2-methyl-4-naphthyl-1-indenyl)titaniumdichloride,dimethylsilylene(2-ethyl-1-indenyl)(2-methyl-4-isopropyl-1-indenyl)titaniumdichloride,dimethylsilylene(2-ethyl-4-phenyl-1-indenyl)(2-ethyl-4-naphthyl-1-indenyl)titaniumdichloride,dimethylsilylene(2-ethyl-4-phenyl-1-indenyl)(2-ethyl-4-isopropyl-1-indenyl)titaniumdichloride,dimethylsilylene(2-ethyl-4-naphthyl-1-indenyl)(2-ethyl-4-isopropyl-1-indenyl)titaniumdichloride, dimethylsilylenebis(2,4,6-trimethyl-1-indenyl)titaniumdichloride, dimethylsilylenebis(4,5,6,7-tetrahydroindenyl)titaniumdichloride, dimethylsilylene(cyclopentadienyl)(fluorenyl)titaniumdichloride, dimethylsilylene(methylcyclopentadienyl)(fluorenyl)-titaniumdichloride, dimethylsilylene(n-butylcyclopentadienyl)(fluorenyl)titaniumdichloride,dimethylsilylene(tetramethylcyclopentadienyl)(indenyl)titaniumdichloride, (tert-butylamido)fluorenyl-1,2-ethanediyltitaniumdichloride, (tert-butylamido)fluorenyl-1,2-ethanediyltitanium dimethyl,(tert-butylamido)fluorenyldimethylsilanetitanium dichloride,(tert-butylamido)fluorenyldimethylsilanetitanium dimethyl, and the like.

Further, in the above-mentioned titanium compound, a compound in whichtitanium is replaced with zirconium or hafnium can be similarlyexemplified.

When a racemic modification and a meso modification exist in theabove-mentioned transition metal compound, the racemic modification ispreferable.

Among these transition metal compounds, the transition metal compoundrepresented by the general formula (4) described below or the transitionmetal compound represented by the general formula (5) described below ispreferable.

(wherein M is a transition metal atom of the Group IV of the PeriodicTable, L¹ is an η⁵-indenyl group or a substituted η⁵-indenyl group, andtwo L¹'s may be mutually the same or different. Y¹ is a carbon atom, asilicon atom, a germanium atom or a tin atom, each of R¹¹ and X¹ is ahydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an arylgroup, a substituted silyl group, an alkoxy group, an aralkyloxy group,an aryloxy group or a heterocyclic group, and all of R¹¹ and X¹ may bethe same or different mutually. p is 1 or 2.)

(wherein M is a transition metal atom of the Group IV of the PeriodicTable, Y² is a silicon atom, a germanium atom or a tin atom, each of(R¹² _(n)—C₅H_(4−n)) and (R¹² _(q)—C₅H_(4−q)) is a substitutedη⁵-cyclopentadienyl group, and each of n and q is an integer of 1 to 3.The respective R¹² may be mutually the same or different, and indicate ahalogen atom, an alkyl group, an aralkyl group, an aryl group, asubstituted silyl group, an alkoxy group, an aralkyloxy group, anaryloxy group or a heterocyclic group. The position and/or kind of R¹²in the substituted η⁵-cyclopentadienyl group is selected so that asymmetric plane including M does not exist. Each of R¹³ and X² is ahydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an arylgroup, a substituted silyl group, an alkoxy group, an aralkyloxy group,an aryloxy group or a heterocyclic group, and all of R¹³ and X² may bethe same or different mutually.)

In the above-mentioned general formula (4) or (5), examples of thetransition metal atom indicated by M include a titanium atom, azirconium atom, a hafnium atom, and the like. A titanium atom or azirconium atom is preferable.

In the above-mentioned general formula (4), L¹ is an η⁵-indenyl group ora substituted η⁵-indenyl group, and two L¹'s may be mutually the same ordifferent. Specific examples of L¹ include an η⁵-indenyl group, anη⁵-methylindenyl group, an η⁵-dimethylindenyl group, anη⁵-n-propylindenyl group, an η⁵-isopropylindenyl group, anη⁵-n-butylindenyl group, an η⁵-tert-butylindenyl group, anη⁵-phenylindenyl group, an η⁵-methylphenylindenyl group, anη⁵-naphthylindenyl group, an η⁵-trimethylsilylindenyl group, anη⁵-tetrahydroindenyl group, and the like.

In the above-mentioned general formula (5), each of (R¹² _(n)—C₅H_(4−n))and (R¹² _(q—C) ₅H_(4−q)) is a substituted η⁵-cyclopentadienyl group,and n and q are an integer of 1 to 3. The respective R¹² may be mutuallythe same or different, and indicate a halogen atom, an alkyl group, anaralkyl group, an aryl group, a substituted silyl group, an alkoxygroup, an aralkyloxy group, an aryloxy group or a heterocyclic group.The position and/or kind of R¹² in the substituted η⁵-cyclopentadienylgroup is selected so that a symmetric plane including M does not exist.

As the halogen atom, a fluorine atom, a chlorine atom, a bromine atomand an iodine atom are exemplified, a chlorine atom or a bromine atom ispreferable, and a chlorine atom is more preferable.

Further, the alkyl group is preferably an alkyl group having 1 to 20carbon atoms, and examples the alkyl group include a methyl group, anethyl group, a n-propyl group, an isopropyl group, a n-butyl group, asec-butyl group, a tert-butyl group, an isobutyl group, an-pentyl group,a neopentyl group, an isoamyl group, a n-hexyl group, a n-octyl group, an-decyl group, a n-dodecyl group, a n-pentadecyl group, a n-eicosylgroup and the like. A methyl group, an ethyl group, an isopropyl group,a tert-butyl group, an isobutyl group, or an amyl group is morepreferable.

All of these alkyl groups may be substituted with a halogen atom such asa fluorine atom, a chlorine atom, a bromine atom or an iodine atom.Examples of the alkyl group having 1 to 10 carbon atoms which issubstituted with a halogen atom include a fluoromethyl group, atrifluoromethyl group, a chloromethyl group, a trichloromethyl group, afluoroethyl group, a pentafluoroethyl group, a perfluoropropyl group, aperfluorobutyl group, a perfluorohexyl group, a perfluorooctyl group, aperchloropropyl group, a perchlorobutyl group, a perbromopropyl groupand the like.

Further, all of these alkyl groups may be partially substituted with analkoxy group such as a methoxy group, an ethoxy group or the like, anaryloxy group such as a phenoxy group or the like or an aralkyloxy groupsuch as a benzyloxy group or the like, etc.

As the aralkyl group, an aralkyl group having 7 to 20 carbon atoms ispreferable. Examples include a benzyl group, a (2-methylphenyl)methylgroup, a (3-methylphenyl)methyl group, a (4-methylphenyl)methyl group, a(2,3-dimethylphenyl)methyl group, a (2,4-dimethylphenyl)methyl group, a(2,5-dimethylphenyl)methyl group, a (2,6-dimethylphenyl)methyl group, a(3,4-dimethylphenyl)methyl group, a (3,5-dimethylphenyl)methyl group, a(2,3,4-timethylphenyl)methyl group, a (2,3,5-timethylphenyl)methylgroup, a (2,3,6-timethylphenyl)methyl group, a(3,4,5-timethylphenyl)methyl group, a (2,4,6-timethylphenyl)methylgroup, a (2,3,4,5-tetramethylphenyl)methyl group, a(2,3,4,6-tetramethylphenyl)methyl group, a(2,3,5,6-tetramethylphenyl)methyl group, a (pentamethylphenyl)methylgroup, an (ethylphenyl)methyl group, a (n-propylphenyl)methyl group, an(isopropylphenyl)methyl group, a (n-butylphenyl)methyl group, a(sec-butylphenyl)methyl group, a (tert-butylphenyl)methyl group, a(n-pentylphenyl)methyl group, a (neopentylphenyl)methyl group, a(n-hexylphenyl)methyl group, a (n-octylphenyl)methyl group, a(n-decylphenyl)methyl group, a (n-dodecylphenyl)methyl group, anaphthylmethyl group, an anthracenylmethyl group and the like, and abenzyl group is more preferable.

All of these aralkyl groups may be partially substituted with a halogenatom such as a fluorine atom, a chlorine atom, a bromine atom or aniodine atom, an alkoxy group such as a methoxy group, an ethoxy group orthe like, an aryloxy group such as a phenoxy group or the like or anaralkyloxy group such as a benzyloxy group or the like, etc.

As the aryl group, an aryl group having 6 to 20 carbon atoms ispreferable. Examples include a phenyl group, a 2-tolyl group, a 3-tolylgroup, a 4-tolyl group, a 2,3-xylyl group, a 2,4-xylyl group, a2,5-xylyl group, a 2,6-xylyl group, a 3,4-xylyl group, a 3,5-xylylgroup, a 2,3,4-trimethylphenyl group, a 2,3,5-trimethylphenyl group, a2,3,6-trimethylphenyl group, a 2,4,6-trimethylphenyl group, a3,4,5-trimethylphenyl group, a 2,3,4,5-tetramethylphenyl group, a2,3,4,6-tetramethylphenyl group, a 2,3,5,6-tetramethylphenyl group, apentamethylphenyl group, an ethylphenyl group, a n-propylphenyl group,an isopropylphenyl group, a n-butylphenyl group, a sec-butylphenylgroup, a tert-butylphenyl group, a n-pentylphenyl group, aneopentylphenyl group, a n-hexylphenyl group, a n-octylphenyl group, an-decylphenyl group, a n-dodecylphenyl group, a n-tetradecylphenylgroup, a naphthyl group, an anthracenyl group and the like, and a phenylgroup is more preferable.

All of these aryl groups may be partially substituted with a halogenatom such as a fluorine atom, a chlorine atom, a bromine atom or aniodine atom, an alkoxy group such as a methoxy group, an ethoxy group orthe like, an aryloxy group such as a phenoxy group or the like or anaralkyloxy group such as a benzyloxy group or the like, etc.

The substituted silyl group is a silyl group substituted with ahydrocarbon group. Examples of the hydrocarbon group include alkylgroups having 1 to 10 carbon atoms such as a methyl group, an ethylgroup, a n-propyl group, an isopropyl group, a n-butyl group, asec-butyl group, a tert-butyl group, an isobutyl group, a n-pentylgroup, a n-hexyl group, a cyclohexyl group and the like, aryl groupssuch as a phenyl group and the like, etc. Examples of the substitutedsilyl group having 1 to 20 carbon atoms include mono-substituted silylgroups having 1 to 20 carbon atoms such as a methylsilyl group, anethylsilyl group, a phenylsilyl group and the like, di-substituted silylgroups having 2 to 20 carbon atoms such as a dimethylsilyl group, adiethylsilyl group, a diphenylsilyl group and the like, tri-substitutedsilyl groups having 3 to 20 carbon atoms such as a trimethylsilyl group,a triethylsilyl group, a tri-n-propylsilyl group, a triisopropylsilylgroup, a tri-n-butylsilyl group, a tri-sec-butylsilyl group, atri-tert-butylsilyl group, a triisobutylsilyl group, atert-butyldimethylsilyl group, a tri-n-pentylsilyl group, atri-n-hexylsilyl group, a tricyclohexylsilyl group, a triphenylsilylgroup and the like, etc. A trimethylsilyl group, atert-butyldimethylsilyl group or a triphenylsilyl group is preferable.

All of these substituted silyl groups may be partially substituted witha halogen atom such as a fluorine atom, a chlorine atom, a bromine atomor an iodine atom, an alkoxy group such as a methoxy group, an ethoxygroup or the like, an aryloxy group such as a phenoxy group or the likeor an aralkyloxy group such as a benzyloxy group or the like, etc.

An alkoxy group having 1 to 20 carbon atoms is preferable as the alkoxygroup, and examples thereof include a methoxy group, an ethoxy group, an-propoxy, an isopropoxy, a n-butoxy group, a sec-butoxy group, atert-butoxy group, a n-pentoxy group, a neopentoxy group, a n-hexoxygroup, a n-octoxy group, a n-dodecoxy group, a n-pentadecoxy group, an-eicosoxy group and the like. A methoxy group, an ethoxy group, anisopropoxy or a tert-butoxy group is more preferable.

All of these alkoxy groups may be partially substituted with a halogenatom such as a fluorine atom, a chlorine atom, a bromine atom or aniodine atom, an alkoxy group such as a methoxy group, an ethoxy group orthe like, an aryloxy group such as a phenoxy group or the like or anaralkyloxy group such as a benzyloxy group or the like, etc.

As the aralkyloxy group, an aralkyloxy group having 7 to 20 carbon atomsis preferable, and examples include a benzyloxy group, a(2-methylphenyl)methoxy group, a (3-methylphenyl)methoxy group, a(4-methylphenyl)methoxy group, a (2,3-dimethylphenyl)methoxy group, a(2,4-dimethylphenyl)methoxy group, a (2,5-dimethylphenyl)methoxy group,a (2,6-dimethylphenyl)methoxy group, a (3,4-dimethylphenyl)methoxygroup, a (3,5-dimethylphenyl)methoxy group, a(2,3,4-trimethylphenyl)methoxy group, a (2,3,5-trimethylphenyl)methoxygroup, a (2,3,6-trimethylphenyl)methoxy group, a(2,4,5-trimethylphenyl)methoxy group, a (2,4,6-trimethylphenyl)methoxygroup, a (3,4,5-trimethylphenyl)methoxy group, a(2,3,4,5-tetramethylphenyl)methoxy group, a(2,3,4,6-tetramethylphenyl)methoxy group, a(2,3,5,6-tetramethylphenyl)methoxy group, a (pentamethylphenyl)methoxygroup, an (ethylphenyl)methoxy group, a (n-propylphenyl)methoxy group,an (isopropylphenyl)methoxy group, (n-butylphenyl)methoxy group, a(sec-butylphenyl)methoxy group, a (tert-butylphenyl)methoxy group, a(n-hexylphenyl)methoxy group, a (n-octylphenyl)methoxy group, a(n-decylphenyl)methoxy group, a naphthylmethoxy group, ananthracenylmethoxy group and the like, and a benzyloxy group is morepreferable.

All of these aralkyloxy groups may be partially substituted with ahalogen atom such as a fluorine atom, a chlorine atom, a bromine atom,an iodine atom or the like, an alkoxy group such as a methoxy group, anethoxy group or the like, an aryloxy group such as a phenoxy group orthe like or an aralkyloxy group such as a benzyloxy group or the like,etc.

As the aryloxy group, an aryloxy group having 6 to 20 carbon atoms ispreferable, and examples include a phenoxy group, a 2-methylphenoxygroup, a 3-methylphenoxy group, a 4-methylphenoxy group, a2,3-dimethylphenoxy group, a 2,4-dimethylphenoxy group, a2,5-dimethylphenoxy group, a 2,6-dimethylphenoxy group, a3,4-dimethylphenoxy group, a 3,5-dimethylphenoxy group, a2-tert-butyl-3-methylphenoxy group, a 2-tert-butyl-4-methylphenoxygroup, a 2-tert-butyl-5-methylphenoxy group, a2-tert-butyl-6-methylphenoxy group, a 2,3,4-trimethylphenoxy group, a2,3,5-trimethylphenoxy group, a 2,3,6-trimethylphenoxy group, a2,4,5-trimethylphenoxy group, a 2,4,6-trimethylphenoxy group, a2-tert-butyl-3,4-dimethylphenoxy group, a2-tert-butyl-3,5-dimethylphenoxy group, a2-tert-butyl-3,6-dimethylphenoxy group, a2,6-di-tert-butyl-3-methylphenoxy group, a2-tert-butyl-4,5-dimethylphenoxy group, a2,6-di-tert-butyl-4-methylphenoxy group, a 3,4,5-trimethylphenoxy group,a 2,3,4,5-tetramethylphenoxy group, a2-tert-butyl-3,4,5-trimethylphenoxy group, a 2,3,4,6-tetramethylphenoxygroup, a 2-tert-butyl-3,4,6-trimethylphenoxy group, a2,6-di-tert-butyl-3,4-dimethylphenoxy group, a2,3,5,6-tetramethylphenoxy group, a 2-tert-butyl-3,5,6-trimethylphenoxygroup, a 2,6-di-tert-butyl-3,5-dimethylphenoxy group, apentamethylphenoxy group, an ethylphenoxy group, a n-propylphenoxygroup, an isopropylphenoxy group, a n-butylphenoxy group, asec-butylphenoxy group, a tert-butylphenoxy group, a n-hexylphenoxygroup, a n-octylphenoxy group, a n-decylphenoxy group, an-tetradecylphenoxy group, a naphthoxy group, an anthracenoxy group andthe like.

All of these aryloxy groups may be partially substituted with a halogenatom such as a fluorine atom, a chlorine atom, a bromine atom, an iodineatom or the like, an alkoxy group such as a methoxy group, an ethoxygroup or the like, an aryloxy group such as a phenoxy group or the likeor an aralkyloxy group such as a benzyloxy group or the like, etc.

The heterocyclic group is a group having a heterocyclic ring, a grouphaving a 4 to 8-membered heterocyclic ring is preferable, and a grouphaving a 4 to 8-membered aromatic heterocyclic ring is more preferable.A hetero atom contained in the heterocyclic ring is preferably anitrogen atom, an oxygen atom or a sulfur atom. Specific examples of theheterocyclic group include, for example, an indolyl group, a furylgroup, a thienyl group, a pyridyl group, a piperidyl group, a quinolylgroup, an isoquinolyl group and the like. Specific examples of theheterocyclic group is more preferably a furyl group.

All of these heterocyclic groups may be partially substituted with ahalogen atom such as a fluorine atom, a chlorine atom, a bromine atom oran iodine atom, an alkoxy group such as a methoxy group, an ethoxy groupor the like, an aryloxy group such as a phenoxy group or the like or anaralkyloxy group such as a benzyloxy group or the like, etc.

R¹² is preferably an alkyl group or a heterocyclic group. Each of n andq is an integer of 1 to 3.

As (R¹² _(n)—C₅H_(4−n)) or (R¹² _(q)—C₅H_(4−q)) having R¹², in which theposition and/or kind of R¹² in the substituted η⁵-cyclopentadienyl groupis selected so that a symmetric plane including M does not exist,examples include a 2-methylcyclopentadienyl group, a2-ethylcyclopentadienyl group, a 2-n-propylcyclopentadienyl group, a2-isopropylcyclopentadienyl group, a 2-n-butylcyclopentadienyl group, a2-isobutylcyclopentadienyl group, a 2-tert-butylcyclopentadienyl group,a 2-n-hexylcyclopentadienyl group, a 3-methylcyclopentadienyl group, a3-ethylcyclopentadienyl group, a 3-n-propylcyclopentadienyl group, a3-isopropylcyclopentadienyl group, a 3-n-butylcyclopentadienyl group, a3-isobutylcyclopentadienyl group, a 3-tert-butylcyclopentadienyl group,a 3-n-hexylcyclopentadienyl group, a 2,3-dimethylcyclopentadienyl group,a 2,3-diethylcyclopentadienyl group, a 2,3-di-n-propylcyclopentadienylgroup, a 2,3-diisopropylcyclopentadienyl group, a2,3-di-n-butylcyclopentadienyl group, a 2,3-diisobutylcyclopentadienylgroup, a 2,3-di-tert-butylcyclopentadienyl group, a2,3-di-n-hexylcyclopentadienyl group, a 2,4-dimethylcyclopentadienylgroup, a 2,4-diethylcyclopentadienyl group, a2,4-di-n-propylcyclopentadienyl group, a 2,4-diisopropylcyclopentadienylgroup, a 2,4-di-n-butylcyclopentadienyl group, a2,4-diisobutylcyclopentadienyl group, a2,4-di-tert-butylcyclopentadienyl group, a2,4-di-n-hexylcyclopentadienyl group, a 3,5-dimethylcyclopentadienylgroup, a 3,5-diethylcyclopentadienyl group, a3,5-di-n-propylcyclopentadienyl group, a 3,5-diisopropylcyclopentadienylgroup, a 3,5-di-n-butylcyclopentadienyl group, a3,5-diisobutylcyclopentadienyl group, a3,5-di-tert-butylcyclopentadienyl group, a3,5-di-n-hexylcyclopentadienyl group, a 2-ethyl-3-methylcyclopentadienylgroup, a 2-methyl-3-ethylcyclopentadienyl group, a2-methyl-3-n-propylcyclopentadienyl group, a2-methyl-3-isopropylcyclopentadienyl group,2-ethyl-3-isopropylcyclopentadienyl group, a2-methyl-3-n-butylcyclopentadienyl group, a2-methyl-3-isobutylcyclopentadienyl group, a2-methyl-3-tert-butylcyclopentadienyl group, a2-methyl-3-n-hexylcyclopentadienyl group, a2-ethyl-4-methylcyclopentadienyl group, a2-methyl-4-ethylcyclopentadienyl group, a2-methyl-4-n-propylcyclopentadienyl group, a2-methyl-4-isopropylcyclopentadienyl group,2-ethyl-4-isopropylcyclopentadienyl group, a2-methyl-4-n-butylcyclopentadienyl group, a2-methyl-4-isobutylcyclopentadienyl group, a2-methyl-4-tert-butylcyclopentadienyl group, a2-methyl-4-n-hexylcyclopentadienyl group, a3-ethyl-5-methylcyclopentadienyl group, a3-methyl-5-ethylcyclopentadienyl group, a3-methyl-5-n-propylcyclopentadienyl group, a3-methyl-5-isopropylcyclopentadienyl group,3-ethyl-5-isopropylcyclopentadienyl group, a3-methyl-5-n-butylcyclopentadienyl group, a3-methyl-5-isobutylcyclopentadienyl group, a3-methyl-5-tert-butylcyclopentadienyl group, a3-methyl-5-n-hexylcyclopentadienyl group, a2,3,5-trimethylcyclopentadienyl group, a 2,4,5-trimethylcyclopentadienylgroup, a 2-(2-furyl)-3,5-dimethylcyclopentadienyl group, a2-(2-furyl)-4,5-dimethylcyclopentadienyl group, and the like.

In the above-mentioned general formula (4) or (5), each of Y¹ and Y² isa carbon atom, a silicone atom, a germanium atom or a tin atom, and acarbon atom or a silicone atom is preferable, respectively. p in theabove-mentioned general formula (4) is 1 or 2.

In the above-mentioned general formula (4) or (5), each of R¹¹, R¹³ andX is a hydrogen atom, a halogen atom, an alkyl group, an aralkyl group,an aryl group, a substituted silyl group, an alkoxy group, an aralkyloxygroup, an aryloxy group or a heterocyclic group, and two R¹¹'s, R¹³'s,X¹'s and X²'s may be respectively the same or different mutually.Wherein the halogen atom, the alkyl group, the aralkyl group, the arylgroup, the substituted silyl group, the alkoxy group, the aralkyloxygroup, the aryloxy group and the heterocyclic group are respectively thesame as those already illustrated as R¹².

As R¹¹ or R¹³, a hydrogen atom or an alkyl group is preferable,respectively.

As X¹ or X², a halogen atom, an alkyl group, an aralkyl group or analkoxy group is preferable.

One of these transition metal compounds may be used alone, or two ormore may be used in combination.

These specific examples can mention a transition metal compoundsatisfying the general formula (4) or (5) among the fore-mentionedspecific examples.

(C) Organoaluminum Compound

As the organoaluminum compound of the component (C) used in the olefinpolymerization catalyst of the present invention, well-knownorganoaluminum compounds can be used. An organoaluminum compoundindicated by the general formula (6) is preferable.R_(c)AlY_(3−c)  (6)(wherein R represents a hydrocarbon group having 1 to 8 carbon atoms, Yrepresents a hydrogen atom and/or a halogen atom, and c represents anumber satisfying an equation of 0<c≦3.)

R in the general formula (6) representing the organoaluminum compound ispreferably an alkyl, and specific examples include a methyl group, anethyl group, a n-propyl group, a n-butyl group, an isobutyl group, an-hexyl group, a 2-methylhexyl group, a n-octyl group and the like, anda methyl group, an ethyl group, a n-butyl group, an isobutyl group and an-hexyl group are preferable. When Y is a halogen atom, specificexamples include a fluorine atom, a chlorine atom, a bromine atom and aniodine atom, and a chlorine atom is preferable.

Specific examples of the organoaluminum compound represented by theabove-mentioned general formula (6) include trialkylaluminums such astrimethylaluminum, triethylaluminum, tri-n-propylaluminum,tri-n-butylaluminum, triisobutylaluminum, tri-n-hexylaluminum,tri-n-octylaluminum and the like; dialkylaluminum chlorides such asdimethylaluminum chloride, di-n-butylaluminum chloride,diisobutylaluminum chloride, di-n-hexylaluminum chloride and the like;alkylaluminum dichlorides such as methylaluminum dichloride,ethylaluminum dichloride, n-propylaluminum dichloride, n-butylaluminumdichloride, isobutylaluminum dichloride, n-hexylaluminum dichloride andthe like; and dialkylaluminum hydrides such as dimethylaluminum hydride,diethylaluminum hydride, di-n-propylaluminum hydride, di-n-butylaluminumhydride, diisobutylaluminum hydride, di-n-hexylaluminum hydride and thelike, etc.

Among these, trialkylaluminums are preferable and trimethylaluminum,triethylaluminum, tri-n-butylaluminum, triisobutylaluminum ortri-n-hexylaluminum is more preferable.

These organoaluminum compounds may be used alone or in combination of 2or more kinds.

(D) Boron Compound

As the boron compound (D) in the present invention, there can be usedany one of (D1) a boron compound represented by the general formulaBQ¹Q²Q³, (D2) a boron compound represented by the general formulaG⁺(BQ¹Q²Q³Q⁴)⁻ and (D3) a boron compound represented by the generalformula (L—H)⁺(BQ¹Q²Q³Q⁴)⁻.

In the boron compound (D1) represented by the general formula BQ¹Q²Q³, Brepresents a boron atom in the trivalent valence state; Q¹ to Q³ may bethe same or different and represent a halogen atom, a hydrocarbon group,a halogenated hydrocarbon group, a substituted silyl group, an alkoxygroup or a di-substituted amino group. Each of Q¹ to Q³ is preferably ahalogen atom, a hydrocarbon group having 1 to 20 carbon atoms, ahalogenated hydrocarbon group having 1 to 20 carbon atoms, a substitutedsilyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20carbon atoms or an amino group having 2 to 20 carbon atoms, morepreferably a hydrocarbon group having 1 to 20 carbon atoms or ahalogenated hydrocarbon group having 1 to 20 carbon atoms.

Specific examples of the compound (D1) includetris(pentafluorophenyl)borane, tris(2,3,5,6-tetrafluorophenyl)borane,tris(2,3,4,5-tetrafluorophenyl)borane,tris(3,4,5-trifluorophenyl)borane, tris(2,3,4-trifluorophenyl)borane,phenylbis(pentafluorophenyl) borane, etc., most preferablytris(pentafluorophenyl) borane.

In the boron compound (D2) represented by the general formulaG⁺(BQ¹Q²Q³Q⁴)⁻, G⁺ represents an inorganic or organic cation; Brepresents a boron atom in the trivalent valence state; and Q¹ to Q⁴ areas defined in Q¹ to Q³.

Specific examples of G⁺ as an inorganic cation in the compoundrepresented by the general formula G⁺(BQ¹Q²Q³Q⁴)⁻ include ferroceniumcation, alkyl-substituted ferrocenium cation, silver cation, etc.

Examples of the G⁺ as an organic cation include triphenylmethyl cation.G⁺ is preferably a carbenium cation, particularly a triphenylmethylcation.

Examples of (BQ¹Q²Q³Q⁴)⁻ include tetrakis(pentafluorophenyl)borate,tetrakis(2,3,5,6-tetrafluorophenyl)borate,tetrakis(2,3,4,5-tetrafluorophenyl)borate,tetrakis(3,4,5-trifluorophenyl)borate,tetrakis(2,3,4-trifluorophenyl)borate,phenyltris(pentafluorophenyl)borate,tetrakis(3,5-bistrifluoromethylphenyl)borate, etc.

Specific combinations of them includeferroceniumtetrakis(pentafluorophenyl)borate,1,1′-dimethylferroceniumtetrakis(pentafluorophenyl)borate,silvertetrakis(pentafluorophenyl)borate,triphenylmethyltetrakis(pentafluorophenyl)borate,triphenylmethyltetrakis(3,5-bistrifluoromethylphenyl)borate, etc., mostpreferably triphenylmethyltetrakis(pentafluorophenyl)borate.

In the boron compound (D3) represented by the formula(L—H)⁺(BQ¹Q²Q³Q⁴)⁻, L represents a neutral Lewis base; (L—H)⁺ representsa Brfnsted acid; B represents a boron atom in the trivalent valencestate; and Q¹ to Q⁴ are as defined in Q¹ to Q³.

Specific examples of (L—H)⁺ as a Brfnsted acid in the compoundrepresented by the formula (L—H)⁺(BQ¹Q²Q³Q⁴)⁻ includetrialkyl-substituted ammoniums, N,N-dialkylaniliniums, dialkylammoniums,triarylphosphoniums, etc., and examples of (BQ¹Q²Q³Q⁴)⁻ include those asdefined above.

Specific combination of them includetriethylammoniumtetrakis(pentafluorophenyl)borate,tripropylammoniumtetrakis(pentafluorophenyl)borate,tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate,tri(n-butyl)ammoniumtetrakis(3,5-bistrifluoromethylphenyl)borate,N,N-dimethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-diethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-2,4,6-pentamethylaniliniumtetrakis(pentafluorophenyl)borate,N,N-dimethylaniliniumtetrakis(3,5-bistrifluoromethylphenyl)borate,diisopropylammoniumtetrakis(pentafluorophenyl)borate,dicyclohexylammoniumtetrakis(pentafluorophenyl)borate,triphenylphosphoniumtetrakis(pentafluorophenyl)borate,tri(methylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate,tri(dimethylphenyl)phosphoniumtetrakis(pentafluorophenyl)borate, etc.,most preferably tri(n-butyl)ammoniumtetrakis(pentafluorophenyl)borate orN,N-dimethylanilinumtetrakis(pentafluorophenyl)borate.

The amount ratio (molar ratio) of respective catalyst components used inthe present invention is not specifically limited. The molar ratio ofthe modified aluminum oxy compound of component (A) to the transitionmetal compound of component (B) [(A)/(B)] is preferably in the range of1/1 to 10000/1, and more preferably 1/1 to 5000/1.

When the organoaluminum compound of component (C) is used, the molarratio of (B) to (C) [(B)/(C)] is preferably in the range of 1/0.1 to1/10000, more preferably 1/1 to 1/5000 and most preferably 1/1 to1/1000.

When the boron compound of component (D) is used, the molar ratio of (B)to (D) [(B)/(D)] is preferably in the range of 1/0.01 to 1/100, morepreferably 1/0.5 to 1/10.

A method of supplying respective catalyst components into apolymerization reactor is not specifically limited. The modifiedaluminum oxy compound (A), the transition metal compound (B), ifnecessary, further, the organoaluminum compound (C), if necessary,moreover, the boron compound (D) may be charged after previouslycontacted, and may be separately charged in the reactor. After contactof arbitrary two components among these, the remaining component (s) maybe contacted.

When the respective components are used in a solution, each of theconcentrations of the modified aluminum oxy compound (A) and theorganoaluminum compound (C) is usually 0.0001 to 100 mol/L in terms ofAl atom, and preferably 0.01 to 10 mol/L, respectively. Theconcentration of the transition metal compound (B) is usually 0.0001 to100 mmol/L in terms of the transition metal atom, and preferably 0.01 to50 mmol/L. The concentration of the boron compound (D) is usually 0.001to 500 mmol/L in terms of the boron atom, and preferably 0.01 to 250mmol/L.

The method of supplying each of the catalyst components in a reactor isnot specifically limited. There is illustrated a method of supplyingeach of the components in a solid condition, a method of charging eachof the components as a solution in which it is dissolved in ahydrocarbon solvent or in a slurry state in which it is suspended, orthe like.

The polymerization process is not specifically limited, and includes asolvent polymerization using an aliphatic hydrocarbon such as butane,pentane, hexane, heptane, octane or the like; an aromatic hydrocarbonsuch as toluene or the like; or a halogenated hydrocarbon such asmethylene dichloride or the like, as a solvent, or a slurrypolymerization, a bulk polymerization which is carried out in a liquidmonomer, a gas phase polymerization in which polymerization is conductedin a gaseous monomer, a high-pressure process in which polymerization isconducted in a supercritical fluid condition of a monomer under hightemperature and high pressure, or the like. As the polymerizationprocess, both of a batch-wise polymerization and a continuouspolymerization are possible.

The polymerization temperature is usually −50° C. to 300° C. andpreferably −20° C. to 250° C. The polymerization pressure is usually 0.1to 300 MPa, preferably 0.1 to 200 MPa, and more preferably 0.1 to 100MPa. In general, the polymerization time is appropriately determinedaccording to the kind of a desired polymer and a reaction apparatus, and1 minute to 20 hours can be adopted.

The polymerization catalyst of the present invention can be applied topolymerization of olefins. As monomers which can be applied, olefins anddiolefins having 2 to 20 carbon atoms and the like can be used, andethylene and α-olefins having 3 to 20 carbon atoms are preferable. Twoor more monomers can also be used, simultaneously. These specificexamples include ethylene, α-olefins such as propylene, 1-butene,1-pentene, 4-methyl-1-pentene, 5-methyl-1-hexene, 1-hexene, 1-heptene,1-octene, 1-nonene, 1-decene and vinylcyclohexane, cyclic olefins suchas norbornene, diolefins such as 1,3-butadiene, 1,4-heptadiene,1,5-hexadiene, 1,7-octadiene and 5-ethylidene-2-norbornene, and thelike. The present invention can be applied to the homopolymerization orcopolymerization of these olefins. Specific examples of the monomersconstituting a copolymer include ethylene-α-olefin having 3 to 20 carbonatoms such as ethylene-propylene, ethylene-1-butene, ethylene-1-hexeneand the like, said α-olefins such as propylene-1-butene and the like,but the present invention should not be limited thereto.

Further, as the olefin copolymer applying the catalyst forpolymerization of the present invention, a copolymer of ethylene with anα-olefin (so called LLDPE, namely a linear low density polyethylene) issuitable in particular. Further, as the olefin polymer applying thecatalyst for polymerization of the present invention, a homopolymer ofan α-olefin, particularly, a homopolymer of propylene or 1-butene issuitable. Particularly, when 1-butene is polymerized using the catalystfor polymerization of the present invention, a homopolymer of 1-buteneof ultra high molecular weight can be obtained.

Moreover, the use of the catalyst for α-olefin polymerization capable ofproducing an α-olefin polymer excellent in stereoregularity is suitableas a process for producing an isotactic stereoregular α-olefin polymerand is particularly suitable as a process for producing an isotacticstereoregular propylene polymer.

Specific examples of the isotactic stereoregular propylene polymerinclude a homopolymer of propylene, a copolymer of propylene with acomonomer such as ethylene and/or an α-olefin having 4 to 12 carbonatoms or the like in an amount of degree not losing crystallinity, etc.The amount of degree not losing crystallinity differs depending on thekind of comonomer, and for example, the amount of the repeating unitderived from ethylene in a copolymer is usually 10% by weight or less incase of ethylene, and the amount of the repeating unit derived from anα-olefin in a copolymer is usually 30% by weight or less in case of theα-olefin other than propylene such as 1-butene or the like. For example,a random copolymer and a block copolymer are exemplified in case of thecopolymer.

Furthermore, the polymerization catalyst of the present invention can bealso applied to homopolymerization of an alkenyl aromatic hydrocarbon orto copolymerization of an alkenyl aromatic hydrocarbon and an olefin.

Alkenyl aromatic hydrocarbon polymers of high molecular weight areproduced with a high activity by using the polymerization catalyst ofthe present invention.

Specific examples of the alkenyl aromatic hydrocarbon include alkylstyrenes such as p-methylstyrene, m-methylstyrene, o-methylstyrene,p-ethylstyrene, m-ethylstyrene, o-ethylstyrene, 2,4-dimethylstyrene,2,5-dimethylstyrene, 3,4-dimethyl styrene, 3,5-dimethyl styrene,3-methyl-5-ethylstyrene, p-tert-butylstyrene, p-sec-butylstyrene and thelike, alkenyl benzenes such as styrene, 2-phenylpropylene,2-phenylbutene and the like, bisalkenyl benzenes such as divinylbenzeneand the like, vinylnaphthalenes such as 1-vinylnaphthalene and the like.And, styrene, p-methylstyrene, m-methylstyrene, o-methylstyrene,p-tert-butylstyrene, 2-phenylpropylene, divinylbenzene and1-vinylnaphthalene are preferred, and, among these, styrene isparticularly preferred. As olefins, the olefins as described above areused.

A chain transfer agent such as hydrogen or the like can also be added toadjust the molecular weight of the polymer.

The present invention is illustrated in detail according to Examples andComparative Examples below, but not limited thereto.

Properties of the olefin polymers in Examples were measured according tomethods described below.

(1) Intrinsic Viscosity [η]:

It was measured in tetralin solution at 135° C. using an Ubbelohdeviscometer (Unit: dl/g)

(2) Molecular Weight Distribution (Mw/Mn):

It was measured under the conditions described below according to gelpermeation chromatography (GPC). Molecular weight distribution wasrepresented by a ratio of weight average molecular weight (Mw) to numberaverage molecular weight (Mn) (Mw/Mn). Further, the calibration curvewas made using a standard polystyrene.

Measuring conditions of Examples and Comparative Examples as follows:

(2-1)

(in Examples 1-22 and 25-29 and Comparative Examples 1-8, 11 and 12)

-   -   Measurement machine: 150C type, manufactured by Milipore Waters        Co.    -   Column: TSK gel GMH6-HT    -   Measurement temperature: 145° C.    -   Solvent: ortho-dichlorobenzene    -   Sample concentration: 10 mg/10 ml (when the molecular weight is        particularly high, the measurement was carried out at a lowered        concentration.)        (2-2)        (in Examples 23-24 and Comparative Examples 9-10)    -   Measurement machine: 800 Series, manufactured by JASCO Co.    -   Column: Shodex A806M    -   Measurement temperature: 45° C.    -   Solvent: tetrahydrofuran    -   Sample concentration: 0.5 mg/ml        (3) Melting Point of Polymer        (in Examples 11-18 and 20-21 and Comparative Examples 5-8)

It was measured under the conditions below using a differential scanningcalorimeter (DSC) (SSC-5000 series thermal analysis system manufacturedby Seiko Instruments Inc.).

-   -   Heating: 40° C. to 150° C. (10° C./minute), retention for 5        minutes    -   Cooling: 150° C. to 10° C. (5° C./minute), retention for 10        minutes    -   Measurement: 10° C. to 160° C. (heating at 5° C./minute)        (4) Glass Transition Temperature and Melting Point        (in Examples 23-24 and Comparative Examples 9 and 10)

It was measured under the conditions below using a differential scanningcalorimeter (DSC) (DSC-5200 manufactured by Seiko Instruments Inc.).

-   -   Heating: 20° C. to 200° C. (20° C./minute), retention for 10        minutes    -   Cooling: 200° C. to −50° C. (20° C./minute), retention for 10        minutes    -   Measurement: −50° C. to 300° C. (heating at 20° C./minute)        (5) Melting Point of Polymer        (in Examples 26-29 and Comparative Examples 11 and 12)

It was measured under the conditions below using a differential scanningcalorimeter (DSC) (DSC-5200 manufactured by Seiko Instruments Inc.).

-   -   Heating: −50° C. to 200° C. (20° C./minute), retention for 5        minutes    -   Cooling: 200° C. to −50° C. (20° C./minute), retention for 5        minutes    -   Measurement: −50° C. to 300° C. (heating at 20° C./minute)        (6) α-olefin Unit Content of Copolymer

It was determined from the characteristic absorptions of ethylene andα-olefin and indicated in terms of the number of short branches per 1000carbon atoms (SCB) in the copolymer.

(7) ¹³C-NMR Measurement (Isotactic Pentad Fraction (mmmm %))

It was carried out by measuring a solution of 200 mg of a sampledissolved in a mixed solvent of o-dichlorobenzene with deuteratedbenzene (volume ration of o-dichlorobenzene to deuterated benzene:3/1)using a NMR spectrometer (AC-250) manufactured by Bruker Ltd.).

(8) ²⁷Al-solid NMR Spectrum

NMR spectrometer having a super conductive magnet of 7.0T (¹Hobservation frequency of 300 MHz) (ASX-300(WB) manufactured by BrukerLtd.) was used, and a measuring probe having a rotation cell diameter of4 mm was used.

Nitrogen gas was used as a gas for rotating the cell, and themeasurement was carried out after the inner atmosphere of a housing ofthe measuring probe was thoroughly replaced with nitrogen. Modifiedaluminum oxy compounds and aluminum oxy compounds samples were preparedby drying the solution thereof under reduced pressure to remove thesolvent thereby to dry and solidify the solution. In a nitrogen box, thesolid NMR measurement sample was packed in a rotation cell of a diameterof 4 mm for solid NMR measurement in a predetermined amount so that thecell could be stably rotated. The rotation speed of the cell wasadjusted between 12 to 14 kHz, and the measurement was carried out inthe room being adjusted at 20° C. (the measuring temperature was about15 to about 20° C.). As a measurement pulse series, there was used apulse series in which a de-coupler is off in the HPDEC method. The pulsewidth was set to 0.5μ seconds which was narrower than 90° pulse widthused in a solution ²⁷Al-NMR spectrum. The pulse interval was set to 2seconds. The width of the spectrum was set to 800 ppm as a width of thechemical shift of ²⁷Al.

As the standard of the chemical shift, the peak appeared at highermagnetic field side was determined as 7 ppm using an active alumina ofLC column packing. After completion of the measurement, the obtaineddata are subjected to Fourier transfer to obtain an ²⁷Al-solid NMRspectrum. In the obtained ²⁷Al-solid NMR spectrum, the phase andbaseline correction thereof were compensated so that the heights ofbases of the highest magnetic field peak group and the lowest magneticfield peak group among peak groups appeared from a vicinity of −150 ppmto a vicinity of 150 ppm, mutually became the same height, and thespectrum of a part in which no peak is observed in regions −150 ppmunder and 150 ppm over, became parallel to the chemical shift axis (axisof abscissa) as far as possible. The baseline as a standard was drawnbetween bases of the highest magnetic field peak group and the lowestmagnetic field peak group so that it became parallel to the chemicalshift axis (axis of abscissa) as far as possible. A vertical line wasdrawn at 10 ppm to the chemical shift axis (axis of abscissa), and thedistance (length) between the intersecting point of the vertical linewith baseline and the intersecting point of the vertical line with thespectrum was measured. And, when a vertical was drawn at 30 ppm to thechemical shift axis (axis of abscissa), the distance between theintersecting point of the vertical line with the baseline and theintersecting point of the vertical line with the spectrum was measured.

REFERENCE EXAMPLE 1 Synthesis Example ofDimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdimethoxide <Compound 1>

Methanol of 0.131 g (4.1 mmol) was dissolved with 10 ml of anhydrousdiethylether in a Schlenk tube, and then a diethyl ether solution ofmethyl lithium (3.9 ml, 4.1 mmol) having a concentration of 1.05 mol/Lwas added thereto dropwise at −78° C. The resulting reaction solutionwas heated to 20° C., the formation of lithium methoxide was confirmedby the completion of a releasing of a gas, and then was cooled to −78°C. again. An anhydrous dimethyl ether suspension (20 ml) of 0.919 g (2.0mmol) ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride prepared previously in another Schlenk tube was transferredinto the reaction solution above, thereafter the resulting reactionmixture was heated gradually to room temperature. After the thusobtained reaction solution was concentrated, 20 ml of toluene was addedthereto, and then the insoluble matter was removed by filtration. Thefiltrate was concentrated to obtaindimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdimethoxide as a yellow crystal (yield 0.86 g, 95%).

¹H-NMR (270 MHz, C₆D₆) δ 7.26 (m, 2H), 4.13 (s, 6H), 2.33 (s, 3H), 1.97(s, 6H), 1.89 (s, 6H), 1.59 (s, 9H), 0.55 (s, 6H)

EXAMPLE 1

A 100 ml stainless autoclave was replaced with argon, 2.5 mmol (in termsof Al atom) of MMAO3A (toluene solution having an Al concentration of5.9% by weight, hereinafter, may be abbreviated as “MMAO”) manufacturedby TOSOH-AKZO Co., Ltd. of a toluene solution and 0.5 mmol of water werecharged therein, and the mixture was stirred for 10 minutes. Further,0.5 mmol of pentafluorophenol (toluene solution: 2 mol/l) was added, andthe resultant was stirred for 10 minutes. In addition, the ratio H2/H1of the MMAO3A was 0.27 as shown in FIG. 1, the ratio L2/L1 of the driedreaction product of the MMAO3A and water was 0.75 as shown in FIG. 2,and the ratio M2/M1 of the dried modified aluminum oxy compound was 1.26as shown in FIG. 3.

On the other hand, in an egg-plant type flask of a volume of 25 ml inwhich the atmosphere was replaced with argon, 1 ml of purified tolueneand 0.5 μmol of 2,2′-thiobis(4-methyl-6-tert-butylphenoxy)titaniumdichloride were mixed with stirring, and then the solution was chargedinto the fore-mentioned autoclave using a syringe.

After the resulting catalyst solution was stirred at room temperaturefor 10 minutes, 30 g of 1-butene was charged and polymerization wascarried out at 40° C. for 15 minutes. After completion of the reaction,the unreacted 1-butene was purged out, the contents of the autoclavewere charged into about 10-fold acidic methanol, and the precipitatedpolymer was separated by filtration and then dried for about 2 hours at80° C. As a result, 0.17 g of poly(1-butene) was obtained.Polymerization activity (gram of polymer per 1 mol of Ti per 1 hour) was1.34×10⁶ g/mol-Ti·hr. The [η] of the poly(1-butene) was 10.9 dl/g andMw/Mn was 2.0.

EXAMPLE 2

A 100 ml stainless autoclave was replaced with argon, 5 mmol of MMAO ofa toluene solution and 1 mmol of pentafluorophenol (toluene solution: 2mol/l) were added, and the mixture was stirred for 10 minutes. Further,1 mmol of water was added, and the mixture was stirred for 10 minutes.

In addition, the ratio H2/H1 of the MMAO3A was 0.27 as shown in FIG. 1,the ratio N2/N1 of the dried reaction product of the MMAO3A andpentafluorophenol was 0.57 as shown in FIG. 4, and the ratio M2/M1 ofthe dried modified aluminum oxy compound was 0.70 as shown in FIG. 5.

On the other hand, in an egg-plant type flask of a volume of 25 ml inwhich the atmosphere was replaced with argon, 5 ml of purified tolueneand 2.5 μmol of 2,2′-thiobis(4-methyl-6-tert-butylphenoxy)titaniumdichloride were mixed with stirring, and then the solution was chargedinto the fore-mentioned autoclave using a syringe.

After the resulting catalyst solution was stirred at room temperaturefor 10 minutes, 30 g of 1-butene was charged and polymerization wascarried out at 40° C. for 15 minutes. After completion of the reaction,the unreacted 1-butene was purged out, the content of the autoclave wascharged into about 10-fold acidic methanol, and the precipitated polymerwas separated by filtration and then dried at 80° C. for about 2 hours.As a result, 0.61 g of poly(1-butene) was obtained. Polymerizationactivity was 9.80×10⁵ g/mol-Ti·hr. The [η] of the poly(1-butene) was10.2 dl/g and Mw/Mn was 2.0.

COMPARATIVE EXAMPLE 1

A 100 ml stainless autoclave was replaced with argon, 5 mmol of MMAO ofa toluene solution was added thereto. On the other hand, in an egg-planttype flask of a volume of 25 ml in which the atmosphere was replacedwith argon, 5 ml of purified toluene and 2.5 μmol of2,2′-thiobis(4-methyl-6-tert-butylphenoxy)titanium dichloride were mixedwith stirring, and then the solution was charged into the fore-mentionedautoclave using a syringe. After the resulting catalyst solution wasstirred at room temperature for 10 minutes, 30 g of 1-butene was chargedand polymerization was carried out at 40° C. for 15 minutes. Aftercompletion of the reaction, the 1-butene that was unreacted was purgedout, the content of the autoclave was charged into about 10-fold acidicmethanol, and the precipitated polymer was separated by filtration andthen dried at 80° C. for about 2 hours. As a result, 0.024 g ofpoly(1-butene) was obtained. Polymerization activity was 3.80×10⁴g/mol-Ti·hr. The [η] of the poly(1-butene) was 0.53 dl/g.

COMPARATIVE EXAMPLE 2

A 100 ml stainless autoclave was replaced with argon, 2.5 mmol of MMAOof a toluene solution and 0.5 mmol of water were added thereto, and themixture was stirred for 10 minutes.

On the other hand, in an egg-plant type flask of a volume of 25 ml inwhich the atmosphere was replaced with argon, 1 ml of purified tolueneand 0.5 μmol of 2,2′-thiobis(4-methyl-6-tert-butylphenoxy)titaniumdichloride were mixed with stirring, and then the solution was chargedinto the fore-mentioned autoclave using a syringe. After the resultingcatalyst solution was stirred at room temperature for 10 minutes, 30 gof 1-butene was charged and polymerization was carried out at 40° C. for15 minutes. After completion of the reaction, the unreacted 1-butene waspurged out, the content of the autoclave was charged into about 10-foldacidic methanol, and the precipitated polymer was separated byfiltration and then dried at 80° C. for about 2 hours. As a result,0.055 g of poly(1-butene) was obtained. Polymerization activity was4.37×10⁵ g/mol-Ti·hr. The [η] of the poly(1-butene) was 5.90 dl/g.

COMPARATIVE EXAMPLE 3

A 100 ml stainless autoclave was replaced with argon, 5 mmol of MMAO ofa toluene solution and 1 mmol of pentafluorophenol (toluene solution: 2mol/l) were added thereto, and the mixture was stirred for 10 minutes.

On the other hand, in an egg-plant type flask of a volume of 25 ml inwhich the atmosphere was replaced with argon, 5 ml of purified tolueneand 2.5 μmol of 2,2′-thiobis(4-methyl-6-tert-butylphenoxy)titaniumdichloride were mixed with stirring, and then the solution was chargedinto the fore-mentioned autoclave using a syringe. After the resultingcatalyst solution was stirred at room temperature for 10 minutes, 30 gof 1-butene was charged and polymerization was carried out at 40° C. for15 minutes. After completion of the reaction, the unreacted 1-butene waspurged out, the content of the autoclave was charged into about 10-foldacidic methanol, and the polymer precipitated was separated byfiltration to be dried at 80° C. for about 2 hours. As a result, 0.23 gof poly(1-butene) was obtained. Polymerization activity was 3.65×10⁵g/mol-Ti·hr. The [η] of the poly(1-butene) was 5.16 dl/g.

EXAMPLE 3

Example 1 was repeated except that 0.3 mmol of triphenyl methanol inplace of pentafluorophenol was used. As a result, 0.14 g ofpoly(1-butene) was obtained. Polymerization activity was 1.11×10⁶g/mol-Ti·hr. The [η] of the poly(1-butene) was 6.0 dl/g, and Mw/Mn was1.9.

EXAMPLE 4

Example 1 was repeated except that 0.25 mmol of tricyclohexylmethanol inplace of pentafluorophenol was used. As a result, 0.16 g ofpoly(1-butene) was obtained. Polymerization activity was 1.23×10⁶g/mol-Ti·hr. The [η] of the poly(1-butene) was 7.7 dl/g.

EXAMPLE 5

Example 1 was repeated except that 0.5 mmol of1,1,1,3,3,3-hexafluoroisopropanol in place of pentafluorophenol wasused. As a result, 0.13 g of poly(1-butene) was obtained. Polymerizationactivity was 1.00×10⁶ g/mol-Ti·hr.

EXAMPLE 6

A 100 ml stainless autoclave was replaced with argon, 5 mmol of MMAO ofa toluene solution and 1 mmol of water were added, and the mixture wasstirred for 10 minutes. Further, 1 mmol of pentafluorophenol (toluenesolution: 2 mol/l) was added, and the mixture was stirred for 10minutes.

On the other hand, in an egg-plant type flask of a volume of 25 ml inwhich the atmosphere was replaced with argon, 5 ml of purified tolueneand 2.5 μmol of(tert-butylamido)(tetramethylcyclopentadienyldimethylsilane)titaniumdichloride were mixed with stirring, and then the solution was chargedinto the fore-mentioned autoclave using a syringe. After the resultingcatalyst solution was stirred at room temperature for 10 minutes, 30 gof 1-butene was charged and polymerization was carried out at 40° C. for15 minutes. After completion of the reaction, the unreacted 1-butene waspurged out, the content of the autoclave was charged into about 10-foldacidic methanol, and the precipitated polymer was separated byfiltration and then dried at 80° C. for about 2 hours. As a result, 0.18g of poly(1-butene) was obtained. Polymerization activity was 2.80×10⁵g/mol-Ti·hr. The [η] of the poly(1-butene) was 1.31 dl/g.

COMPARATIVE EXAMPLE 4

A 100 ml stainless autoclave was replaced with argon, 10 mmol of MMAO ofa toluene solution was added thereto.

On the other hand, in an egg-plant type flask of a volume of 25 ml inwhich the atmosphere was replaced with argon, 5 ml of purified tolueneand 10 μmol of(tert-butylamido)(tetramethylcyclopentadienyldimethylsilane)titaniumdichloride were mixed with stirring, and then the solution was chargedinto the fore-mentioned autoclave using a syringe. After the catalystsolution was mixed by stirring at room temperature for 10 minutes, 30 gof 1-butene was charged and polymerization was carried out at 40° C. for60 minutes. After completion of the reaction, the unreacted 1-butene waspurged out, the content of the autoclave was charged into about 10-foldacidic methanol, and the precipitated polymer was separated byfiltration and then dried at 80° C. for about 2 hours. As a result, 0.02g of poly(1-butene) was obtained. Polymerization activity was 2.04×10³g/mol-Ti·hr. The [η] of the poly(1-butene) was 0.50 dl/g.

EXAMPLE 7

Example 6 was repeated except thatisopropylidene(cyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride in place of(tert-butylamido)(tetramethylcyclopentadienyldimethylsilane)titaniumdichloride was used. As a result, 0.60 g of poly(1-butene) was obtained.Polymerization activity was 2.39×10⁵ g/mol-Ti·hr.

EXAMPLE 8

Example 6 was repeated except that pentamethylcyclopentadienyltitaniumtrichloride in place of(tert-butylamido)(tetramethylcyclopentadienyldimethylsilane)titaniumdichloride was used and polymerization time was 30 minutes. As a result,1.07 g of poly(1-butene) and was obtained. Polymerization activity was8.58×10⁵ g/mol-Ti·hr.

EXAMPLE 9

A 1 liter stainless autoclave was replaced with argon, and 200 g of1-butene was charged, 5 mmol of MMAO of a toluene solution and 1 mmol ofwater were added, and the mixture was stirred for 10 minutes. Further, 1mmol of pentafluorophenol (toluene solution: 2 mol/l) was added, and themixture was stirred for 10 minutes.

On the other hand, in an egg-plant type flask of an inner volume of 25ml in which the atmosphere was replaced with argon, 5 ml of purifiedtoluene and 2.5 μmol of(pentamethylcyclopentadienyl)(2,6-diisopropylphenoxy)titanium dichloridewere mixed with stirring, and then the solution was charged into thefore-mentioned autoclave using a syringe.

Polymerization was carried out at 40° C. for 60 minutes. Aftercompletion of the reaction, the unreacted 1-butene was purged out, thecontent of the autoclave was charged into about 10-fold acidic methanol,and the precipitated polymer was separated by filtration and then driedat 80° C. for about 2 hours. As a result, 42.2 g of poly(1-butene) wasobtained. Polymerization activity was 1.69×10⁷ g/mol-Ti·hr. The [η] ofthe poly(1-butene) was 0.97 dl/g and Mw/Mn was 1.8.

EXAMPLE 10

Example 9 was repeated except that the polymerization temperature was 5°C. As a result, 36.2 g of poly(1-butene) was obtained. Polymerizationactivity was 1.45×10⁷ g/mol-Ti·hr. The [η] of the poly(1-butene) was 3.2dl/g and Mw/Mn was 1.8.

EXAMPLE 11

A 0.4 liter stainless autoclave was replaced with argon, 198 ml oftoluene as a solvent and 2 ml of hexene-1 as an α-olefin were chargedand the temperature of the autoclave was raised to 60° C. After raisingthe temperature, ethylene was fed while controlling the pressure at 0.6MPa. After stabilization of the inside of system, 2 mmol of MMAO of atoluene solution and 0.4 mmol of water were added, and the mixture wasmixed by stirring for 10 minutes. Further, 0.4 mmol of pentafluorophenol(toluene solution: 2 mol/l) was added, and the mixture was mixed bystirring for 10 minutes. On the other hand, 1 ml of 1 mmol/L toluenesolution ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride was charged into the fore-mentioned autoclave using asyringe, and polymerization was carried out for 60 minutes. Theunreacted monomer was purged out, the content of the autoclave wascharged into about 10-fold acidic methanol, and the precipitated polymerwas separated by filtration and then dried at 80° C. for about 2 hours.As a result of the polymerization, 5.93 g of ethylene-hexene-1 copolymerhaving an [η] of 4.45 dl/g and a melting point of 68.4° C. was obtained.Polymerization activity was 5.93×10⁶ g/mol-Ti·hr.

COMPARATIVE EXAMPLE 5

A 0.4 liter stainless autoclave was replaced with argon, 198 ml oftoluene as a solvent and 2 ml of 1-hexene as an α-olefin were chargedand the temperature of the autoclave was heated to 60° C. After theheating, ethylene was fed while adjusting the pressure at 0.6 MPa. Afterthe system was stabilized, 2 mmol of MMAO of a toluene solution and 1 mlof 1 mmol/L toluene solution ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride were charged into the fore-mentioned autoclave using asyringe and polymerization was carried out for 60 minutes. The monomerunreacted was purged out, the content of the autoclave was charged intoabout 10-fold acidic methanol, and the precipitated polymer wasseparated by filtration and then dried at 80° C. for about 2 hours. As aresult of the polymerization, 2.16 g of ethylene-1-hexene copolymerhaving an [η] of 1.21 dl/g and melting points of 75.6° C. and 89.5° C.was obtained. Polymerization activity was 2.16×10⁶ g/mol-Ti·hr.

COMPARATIVE EXAMPLE 6

A 0.4 liter stainless autoclave was replaced with argon, 198 ml oftoluene as a solvent and 2 ml of 1-hexene as an α-olefin were chargedand the temperature of the autoclave was heated to 60° C. After theheating, ethylene was fed while adjusting the pressure at 0.6 MPa. Afterthe system was stabilized, 2 mmol of MMAO of a toluene solution and 0.4mmol of water were added, and the mixture was stirred for 10 minutes.

On the other hand, 1 ml of 1 mmol/L toluene solution ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride was charged into the fore-mentioned autoclave using a syringeand polymerization was carried out for 60 minutes. The unreacted monomerwas purged out, the content of the autoclave was charged into about10-fold acidic methanol, and the precipitated polymer was separated byfiltration and then dried at 80 for about 2 hours. As a result of thepolymerization, 0.84 g of ethylene-1-hexene copolymer having an [η] of1.54 dl/g and a melting point of 91.5° C. was obtained. Polymerizationactivity was 8.40×10⁵ g/mol-Ti·hr.,

EXAMPLE 12

Example 11 was repeated except that 2 μmol ofbiscyclopentadienyltitanium dichloride in place ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride was used. As a result of the polymerization, 9.62 g ofethylene-1-hexene copolymer having an [η] of 2.00 dl/g and a meltingpoint of 119° C. was obtained. Polymerization activity was 4.81×10⁶g/mmol-Ti·hr.

EXAMPLE 13

Example 11 was repeated except that 2 μmol of(pentamethylcyclopentadienyl)(2,6-diisopropylphenoxy)titanium dichloridein place ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride was used. As a result of the polymerization, 12.17 g ofethylene-1-hexene copolymer having an [η] of 2.78 dl/g and meltingpoints of 51° C. and 113.8° C. was obtained. Polymerization activity was6.09×10⁶ g/mol-Ti·hr.

EXAMPLE 14

Example 11 was repeated except that 2 μmol ofdimethylsilylenebisindenylhafnium dichloride in place ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride was used. As a result of the polymerization, 11.61 g ofethylene-1-hexene copolymer having an [η] of 2.25 dl/g and meltingpoints of 71° C. and 112° C. was obtained. Polymerization activity was5.8×10⁶ g/mol-Hf·hr.

EXAMPLE 15

Example 11 was repeated except that 5 μmol ofhydrotris(3,5-dimethylpyrazolylborate)titanium trichloride in place ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdichloride, 10 mmol of MMAO, 2 mmol of water and 2 mmol ofpentafluorophenol (toluene solution: 2 mol/l) were used andpolymerization temperature was 80° C. As a result of the polymerization,2.61 g of ethylene-1-hexene copolymer having an [η] of 1.42 dl/g and amelting point of 110.7° C. was obtained. Polymerization activity was5.22×10⁵ g/mol-Ti·hr.

EXAMPLE 16

Example 15 was repeated except thathydrotris(3,5-dimethylpyrazolylborate)zirconium trichloride in place ofhydrotris(3,5-dimethylpyrazolylborate)titanium trichloride was used. Asa result of the polymerization, 9.62 g of ethylene-1-hexene copolymerhaving an [η] of 1.51 dl/g and a melting point of 123.5° C. and 112° C.was obtained. Polymerization activity was 1.92×10⁶ g/mol-Zr·hr.

EXAMPLE 17

A dropping funnel was set on a 100 ml four-necked flask, the flask wasreplaced with nitrogen and then, a thermometer was set. 10 ml of heptaneas a solvent, and 20 mmol of MMAO3A (manufactured by TOSOH-AKZO Co.,Ltd.; heptane solution having an Al concentration of 7.0% by weight)were charged in the flask and the mixture was stirred. To the droppingfunnel, 144 μl (8 mmol) of water deaerated with nitrogen and 10 ml oftoluene were charged and slowly added dropwise into the flask. Aftercompletion of the dropwise addition, the dropping funnel was rinsed with5 ml of toluene and the mixture was stirred at 25 to 30° C. for 30minutes. Then, 4 ml (toluene solution: 2 mol/l) of pentafluorophenol and10 ml of toluene were charged to the dropping funnel, and slowly addeddropwise into the flask. After completion of the dropwise addition, thedropping funnel was rinsed with 5 ml of toluene and the mixture wasstirred at 25 to 30° C. for 1 hour. The reaction solution wasconcentrated under vacuum to remove the solvent and obtain a white solid(compound A).

A 0.4 liter autoclave reactor equipped with a stirrer was replaced withargon, then 185 ml of cyclohexane as a solvent and 15 ml of 1-hexene asan α-olefin were charged, and the reactor was heated to 180° C. Afterthe heating, ethylene was fed while adjusting the pressure at 2.5 MPa.After the system was stabilized, 50.6 mg (equivalent to 0.41 mmol interms of Al atom) of the above-mentioned compound A and 0.5 ml (namely,0.5 μmol ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdimethoxide (compound 1) and 25 μmol of triisobutylaluminum) of aheptane solution (the concentration of compound 1 is 1 μmol/ml and theconcentration of triisobutylaluminum is 50 μmol/ml, and a molar ratio ofAl atom to Ti atom was adjusted at 50) in which the compound 1 andtriisobutylaluminum are mixed, were charged thereto. Polymerization wascarried out for 2 minutes. As a result of the polymerization, 1.38 g ofethylene-1-hexene copolymer having an [η] of 2.12 dl/g and meltingpoints of 79.5° C. and 83° C. was obtained. Polymerization activity per1 mol of Ti atom was 2.7×10⁶ g/mol-Ti per 2 minutes (8.1×10⁷g/mol-Ti·hr).

EXAMPLE 18

A dropping funnel was set on a 200 ml four-necked flask, the flask wasreplaced with nitrogen and then, a thermometer was set. 12 ml of heptaneas a solvent and 20 mmol of MMAO3A (manufactured by TOSOH-AKZO Co.,Ltd.; heptane solution having an Al concentration of 7.0% by weight)were charged to the flask and the mixture was stirred. To the droppingfunnel, 72 μl (4 mmol) of water deaerated with nitrogen and 5 ml oftoluene were charged and slowly added dropwise into the flask. Aftercompletion of the dropwise addition, the dropping funnel was washed with5 ml of toluene and the mixture was stirred at 25 to 30° C. for 30minutes. Then, 8 ml (toluene solution: 2 mol/l) of pentafluorophenol wascharged to the dropping funnel and added dropwise thereto at 25 to 30°C., and the mixture was stirred at 25 to 30° C. for 1 hour. A whiteslurry was obtained. (Al concentration: 0.5 mol/L) (compound B)

A 0.4 liter autoclave reactor equipped with a stirrer was replaced withargon, then 185 ml of cyclohexane as a solvent and 15 ml of 1-hexene asan α-olefin were charged, and the reactor was heated to 180° C. Afterthe heating, ethylene was fed while adjusting the pressure at 2.5 MPa.After the system was stabilized, 2 ml (equivalent to 1 mmol, in terms ofAl atom) of the above-mentioned compound B and 0.5 ml (namely, 0.5 μmolofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdimethoxide (compound 1) and 25 μmol of triisobutylaluminum) of aheptane solution (the concentration of compound 1 is 1 μmol/ml and theconcentration of triisobutylaluminum is 50 μmol/ml, and a molar ratio ofAl atom to Ti atom was adjusted at 50) in which the compound 1 andtriisobutylaluminum were mixed, were charged thereto. Polymerization wascarried out for 2 minutes. As a result of the polymerization, 3.65 g ofethylene-1-hexene copolymer having an [η] of 1.59 and melting points of73.3° C. and 84.9° C. was obtained. Polymerization activity per 1 mol ofTi atom was 7. 3×10⁶ g/mol-Ti per 2 minutes (2.19×10⁸ g/mol-Ti·hr).

EXAMPLE 19

A 1 liter stainless autoclave was replaced with argon, 200 ml of toluenewas charged and the temperature of the autoclave was heated to 60° C.After the heating, ethylene was fed while adjusting the pressure at 0.6MPa. After the system was stabilized, 5 mmol of MMAO of a toluenesolution and 1 mmol of water were added, and the mixture was stirred for10 minutes. Further, 1 mmol of pentafluorophenol (toluene solution: 2mol/l) was added, and the mixture was stirred for 10 minutes.

On the other hand, 5 ml of 0.5 mmol/L toluene solution of2,6-bis-[1-(2,6-diisopropylphenylimino)ethyl]pyridineiron dichloride wascharged into the fore-mentioned autoclave using a syringe, andpolymerization was carried out for 60 minutes. The monomer unreacted waspurged out, the content of the autoclave was charged into about 10-foldacidic methanol, and the precipitated polymer was separated byfiltration and then dried at 80° C. for about 2 hours. As a result ofthe polymerization, 2.40 g of polyethylene having an [η] of 1.57 dl/gwas obtained. Polymerization activity 9.62×10⁵ g/mol-Fe·hr.

EXAMPLE 20

A dropping funnel was set on a 200 ml four-necked flask, the flask wasreplaced with nitrogen and then, a thermometer was set. 10 ml of heptaneas a solvent and 20 ml of MMAO3A (manufactured by TOSOH-AKZO Co., Ltd.;heptane solution having an Al concentration of 7.0% by weight) werecharged to the flask and the mixture was stirred. To the droppingfunnel, 144 μl (8 mmol) of water deaerated with nitrogen and 0 ml oftoluene were charged and slowly added dropwise into the flask. Aftercompletion of the dropwise addition, the dropping funnel was washed with5 ml of toluene and the mixture was stirred at 25 to 30° C. for 30minutes. Then, 4 ml (toluene solution: 2 mol/l) of pentafluorophenol and10 ml of toluene were charged to the dropping funnel and added dropwiseto the flask at 25 to 30° C., After completion of the dropwise addition,the dropping funnel was washed with 5 ml of toluene and the mixture wasstirred at 25 to 30° C. for 1 hour. The reaction solution wasconcentrated under reduced pressure to obtain a white solid (compoundC).

A 0.4 liter autoclave reactor equipped with a stirrer was replaced withargon, then 185 ml of cyclohexane as a solvent and 15 ml of 1-hexene asan α-olefin were charged, and the reactor was heated to 180° C. Afterthe heating, ethylene was fed while adjusting the pressure at 2.5 MPa.After the system was stabilized, 48.9 mg (equivalent to 0.40 mmol, interms of Al atom) of the above-mentioned compound C, 0.5 ml of a mixedheptane solution ofdimethylsilylene(tetramethylcyclopentadienyl)(3-tert-butyl-5-methyl-2-phenoxy)titaniumdimethoxide (compound 1) and 25 μmol of triisobutylaluminum (theconcentration of compound 1 is 1 μmol/ml, the concentration oftriisobutylaluminum is 50 μmol/ml, and the molar ratio of Al atom to Tiatom was adjusted at 50) (namely, the compound 1 is 0.5 μmol, andtriisobutylaluminum is 25 μmol), and 1. 5 ml of a heptane slurry ofN,N′-dimethylanilinium (tetrakispentafluorophenyl)borate (compound 2)(concentration; 1 μmol/ml) were charged thereto. Polymerization wascarried out for 2 minutes. As a result of the polymerization, 6.5 g ofethylene-1-hexene copolymer having an [η] of 1.06 dl/g, SCB of 35.3, Mwof 63400, Mw/Mn of 3.4 and melting points of 75.2° C. and 83.4° C. wasobtained. Polymerization activity per 1 mol of Ti atom was 1.3×10⁷g/mol-Ti per 2 minutes (3.9×10⁸ g/mol-Ti·hr).

EXAMPLE 21

A 0.4 liter stainless autoclave was replaced with argon, 185 ml ofcyclohexane as a solvent and 15 ml of 1-hexene as an α-olefin werecharged and the reactor was heated to 180° C. After the heating,ethylene was fed while adjusting the pressure at 2.5 MPa. After thesystem was stabilized, 0.1 mmol of triisobutyl aluminum, 0.2 ml (0.1mmol in terms of Al atom) of the slurry of compound B prepared inExample 18 and 0.5 ml of a heptane mixed solution of compound 1 andtriisobutyl aluminum (concentration of compound 1; 1 μmol/ml,concentration of triisobutyl aluminum; 50 μmol/ml, molar ratio of Alatom to Ti atom (Al/Ti); 50) (namely 0.5 μmol of compound 1 and 25 μmolof triisobutyl aluminum), 1.5 ml of a heptane-slurry of the compound 2(concentration; 1 μmol/ml) were added into the autoclave. Polymerizationwas carried out for 2 minutes.

As a result of the polymerization, 3.07 g of ethylene-1-hexene copolymerhaving an [η] of 1.11 dl/g, SCB of 30.4, Mw of 52100, Mw/Mn of 2.4, andmelting points of 80.8° C. and 92.7° C. was obtained. Polymerizationactivity per 1 mol of Ti atom was 6.1×10⁶ g/mol-Ti per 2 minutes(183×10⁸ g/mol-Ti·hour).

EXAMPLE 22

A dropping funnel was set on a 100 ml four-necked flask, the flask wasreplaced with nitrogen and then, a thermometer was set. As a solvent, 8ml of heptane as a solvent and 10 mmol of MMAO3A (manufactured by TOSOAKZO Co., Ltd.; 2 mol/l) were charged in the flask and the mixture wasstirred. To the dropping funnel, 72 μl (4 mmol) of water deaerated withnitrogen and 5 ml of toluene were charged and slowly added dropwise intothe flask. After completion of the dropwise addition, the droppingfunnel was rinsed with 5 ml of toluene and the mixture was stirred at 25to 30° C. for 30 minutes.

Then, 2 ml (toluene solution: 2 mol/l) of pentafluorophenol and 10 ml oftoluene were charged to the dropping funnel, and slowly added dropwiseat 25 to 30° C. into the flask. After completion of the dropwiseaddition, the mixture was stirred at 25 to 30° C. for 2 hours. A whiteslurry (concentration:0.67 mol/l in terms of Al atom) (Compound D) wasobtained.

A 0.4 liter autoclave reactor equipped with a stirrer was replaced withargon, then 140 ml of cyclohexane as a solvent and 60 ml of 1-hexene asan α-olefin were charged, and the reactor was heated to 180° C. Afterthe heating, ethylene was fed while adjusting the pressure at 2.5 MPa.After the system was stabilized, 1.5 ml of slurry of the compound D(equivalent to 1 mmol in terms of Al atom), 1 ml of a toluene solutionof bis(n-butyl cyclopentadienyl)zirconium dichloride (concentration; 1μmol/ml) and 3 ml of a heptane slurry of the compound 2 (concentration;1μmol/ml) were added into the reactor. Polymerization was carried out for2 minutes. As a result of polymerization, 5.7 g of an, ethylene-1-hexenecopolymer was obtained. Polymerization activity per 1 mol of Zr atom was5.7×10⁶ g/mol-Zr per 2 minutes (1.71×10⁸ g/mol-Zr/hour).

COMPARATIVE EXAMPLE 7

A 0.4 liter stainless autoclave was replaced with argon, 185 ml ofcyclohexane as a solvent and 15 ml of 1-hexene as an α-olefin werecharged and the autoclave was heated to 180° C. After the heating,ethylene was fed while adjusting the pressure at 2.5 MPa. After thesystem was stabilized, 0.2 mmol of triisobutylaluminum, 0.5 ml of aheptane mixed solution of the compound 1 and triisobutylaluminum(concentration of the compound 1; 1 μmol/ml, concentration oftriisobutylaluminum; 50 μmol/ml) (namely, 0.5 μmol of compound 1 and 25μmol of triisobutylaluminum) were added thereinto, and subsequently 1.5ml of a heptane slurry of the compound 2 (slurry concentration of 1μmol/ml) was added. Polymerization was carried out for 2 minutes. As aresult of the polymerization, 2.33 g of ethylene-1-hexene copolymerhaving an [η] of 1.04 dl/g and SCB of 31.7, Mw of 56500, Mw/Mn of 1.9and melting points of 78.3° C. and 89.9° C. was obtained. Polymerizationactivity per 1 mol of Ti atom was 4.7×10⁶ g/mol-Ti per 2 minutes(1.41×10⁸ g/mol-Ti·hour).

COMPARATIVE EXAMPLE 8

A dropping funnel was set on a 200 ml four-necked flask, the flask wasreplaced with nitrogen and then, a thermometer was set. 10 ml ofheptaneas a solvent and 20 mmol of MMAO3A (manufactured by TOSOH-AKZOCo., Ltd.; 2 mol/l) were charged in the flask and the mixture wasstirred. To the dropping funnel, 360 μl (20 mmol) of water deaeratedwith nitrogen and 5 ml of toluene were charged and slowly added dropwiseinto the flask. After completion of the dropwise addition, the droppingfunnel was rinsed with 5 ml of toluene and the mixture was stirred at 25to 30° C. for 30 minutes. The reaction solution was concentrated underreduced pressure to remove the solvent and obtain a white solid(Compound E).

A 0.4 liter autoclave reactor equipped with a stirrer was replaced withargon, then 185 ml of cyclohexane as a solvent and 15 ml of 1-hexene asan α-olefin were charged, and the reactor was heated to 180° C. Afterthe heating, ethylene was fed while adjusting the pressure at 2.5 MPa.After the system was stabilized, 27.6 mg of the compound E (equivalentto 0.43 mmol in terms of Al atom), 0.5 ml of a heptane mixed solution ofthe compound 1 and triisobutylaluminum (concentration of the compound; 1μmol/ml, concentration of triisobutylaluminum; 50 μmol/ml, molar ratioof Al atom to Ti atom; 50) (namely, 0.5 μmol of compound 1 and 25 μmolof triisobutylaluminum) and 1.5 ml of a heptane slurry of the compound 2(concentration; 1 μmol/ml) were added thereinto. Polymerization wascarried out for 2 minutes. As a result of the polymerization, 2.45 g ofethylene-1-hexene copolymer having an [η] of 0.97 dl/g and SCB of 34.5and melting points of 76.6° C. and 83.8° C. was obtained. Polymerizationactivity per 1 mol of Ti atom was 4.9×10⁶ g/mol-Ti per 2 minutes(1.47×10⁸ g/mol-Ti/hour).

EXAMPLE 23

A 0.4 liter autoclave reactor equipped with a stirrer was replaced withargon, 27 ml of styrene and 83 ml of a purified toluene were charged,and then 0.8 MPa of ethylene was charged therein. Further, 4.4 ml of atoluene solution of MMAO3A and 14 μl of water were mixed in a 50 mlflask replaced with argon and then stirred for 10 minutes, thereafter,0.8 ml of a toluene solution of pentafluorophenol (toluene solution: 2mol/l) was added, and stirred for 10 minutes. The mixture was chargedinto fore-mentioned autoclave, subsequently 3.2 mg ofisopropylidenebis(indenyl)zirconium dichloride dissolved in 6.4 ml oftoluene, was charged into the fore-mentioned autoclave andpolymerization was carried out at 60° C. for 1 hour.

Thereafter, thus obtained reaction solution was poured in a mixture of 5ml of hydrochloric acid (12N) and 1000 ml of methanol and then theresulting precipitate was filtered to obtain a white solid. The solidwas washed with methanol and then was dried under reduced pressure toobtain 25.24 g of a polymer. This polymer had a Mn of 65,000, Mw/Mn of2.2, glass transition temperature of 21° C. and melting point of 95° C.

COMPARATIVE EXAMPLE 9

Example 23 was repeated except that 4.4 ml of the toluene solution ofMMAO was charged without mixing with water and pentafluorophenol, toobtain 25.13 g of a polymer. This polymer had a Mn of 58,000, Mw/Mn of2.2, glass transition temperature of 20° C. and melting point of 98° C.

EXAMPLE 24

Example 23 was repeated except that 14 μl of water was changed to 29 μlof water, 3.2 mg of isopropylidenebis(indenyl)zirconium dichloridedissolved in 6.4 ml of a purified toluene was changed to 2.9 mg of(tert-butylamide) (tetramethylcyclopentadienyldimethylsilane)titaniumdichloride dissolved in 5.8 ml of toluene, to obtain 11.36 g of apolymer. This polymer had a Mn of 798,000, Mw/Mn of 2.0, glasstransition temperature of −6° C. and melting point of 78° C. Thispolymer was shaped by pre-heating the polymer at 180° C. for 3 minutes,hot-pressing the pre-heated polymer at a temperature of 180° C. under apressure of 30 to 50 kg/cm² for 3 minutes. A pressed sheet having a sizeof 50 mm×50 mm×0.3 mm had a excellent tensile strength.

COMPARATIVE EXAMPLE 10

Example 24 was repeated except that 4.4 ml of the toluene solution ofMMAO was charged without mixing with water and pentafluorophenol, toobtain 13.04 g of a polymer. This polymer had a Mn of 67,000, Mw/Mn of2.2, glass transition temperature of −6° C. and melting point of 79° C.

EXAMPLE 25

A 100 ml stainless autoclave was replaced with argon, 20 mmol (in termsof Al atom) MMAO3A of a toluene solution, 11 mmol of water and 4 mmol ofpentafluorophenol (toluene solution: 2 mol/l) were simultaneously addedand the resulting mixture was stirred for 10 minutes.

In addition, the ratio H2/H1 of the MMAO3A was 0.27 as shown in FIG. 1,the ratio M2/M1 of the dried modified aluminum oxy compound was 1.04 asshown in FIG. 6.

On the other hand, in an egg-plant type flask of a volume of 25 ml inwhich the atmosphere was replaced with argon, 5 ml of purified tolueneand 2.5 μmol of 2,2′-thiobis(4-methyl-6-tert-butylphenoxy)titaniumdichloride were mixed with stirring, and then the resulting solution wascharged into the autoclave using a syringe. After the resulting catalystsolution was stirred at room temperature for 10 minutes, 30 g of1-butene was charged and polymerization was carried out at 40° C. for 15minutes. After completion of the reaction, the unreacted 1-butene waspurged out, the content of the autoclave was charged into about 10-foldacidic methanol, the resulting precipitated polymer was separated byfiltration and then dried for at 80° C. for about 2 hours. As a result,0.66 g of poly(1-butene) was obtained. Polymerization activity was1.04×10⁶ g/mol-Ti/hr. The [η] of poly(1-butene) was 9.21 dl/g.

EXAMPLE 26

The atmosphere of a 1 liter stainless autoclave was replaced with argon,and 100 g of propylene was charged after charging 300 ml of toluene.Then, after raising a temperature to 40° C., 2.0 mmol (as a molar amountof Al atom) of MMAO3A of a toluene solution manufactured by TOSOH-AKZOCo., Ltd. (an Al concentration of 5.6% by weight; hereinafter, may beabbreviated as “MMAO1”) and 0.2 mmol of water were charged therein bypressurization, and the mixture was mixed by stirring for 10 minutes.Further, 0.4 mmol of pentafluorophenol was charged therein bypressurization, and the mixture was stirred for 10 minutes.

On the other hand, in an egg-plant type flask of an inner volume of 25ml in which the atmosphere was replaced with argon, 5 ml of purifiedtoluene and 1 μmol of dimethylsilylenebis(2-methyl-1-indenyl)zirconiumdichloride were mixed by stirring, and then the solution was chargedinto the fore-mentioned autoclave using a syringe. After carrying outthe polymerization for 1 hour, the polymerization was stopped bycharging 5 ml of methanol. After purging out the unreacted propylene,the contents of the autoclave were charged into about 1000 ml of acidicmethanol, and the precipitated polymer was separated by filtration andthen dried for about 2 hours at 80° C. As a result, 2.2 g of apolypropylene was obtained. The [η] of the polypropylene obtained was2.9 dl/g, Mw/Mn was 2.0, mmmm % was 96.5% and melting point was 153. 9°C. Further, in an ²⁷Al-solid NMR spectrum of a sample obtained by dryingMMAO1 under reduced pressure, the ratio of H2 to H1 was 0.27.

EXAMPLE 27

Polymerization was similarly carried out except that the amount ofpentafluorophenol was changed from 0.4 mmol to 0.6 mmol in Example 26.As a result, 3.2 g of a polypropylene was obtained. The [η] of thepolypropylene obtained was 3.0 dl/g, Mw/Mn was 1.9, mmmm % was 96.3% andmelting point was 153.8° C.

EXAMPLE 28

Polymerization was similarly carried out except that the amount of waterwas changed from 0.2 mmol to 0.4 mmol and the amount ofpentafluorophenol was changed from 0.4 mmol to 0.2 mmol in Example 26.As a result, 15.9 g of a polypropylene was obtained. The [η] of thepolypropylene obtained was 2.8 dl/g, Mw/Mn was 2.0, mmmm % was 95.6% andmelting point was 152.7° C.

Further, in an ²⁷Al-solid NMR spectrum of a sample obtained by drying areaction product obtained by mixing MMAO1 and water (molar ratio 5:1)with stirring, under reduced pressure, the ratio of L2 to L1 was 0.75.

COMPARATIVE EXAMPLE 11

The atmosphere of a 1 liter stainless autoclave was replaced with argon,and 10 g of propylene was charged after charging 300 ml of toluene.Then, after raising a temperature to 40° C., 2.0 mmol of MMAO1 as amolar amount of Al atom was charged therein, and the mixture was mixedby stirring for 10 minutes.

On the other hand, in an egg-plant type flask of an inner volume of 25ml in which the atmosphere was replaced with argon, 5 ml of purifiedtoluene and 1 μmol of dimethylsilylenebis(2-methyl-1-indenyl)zirconiumdichloride were mixed by stirring, and then the solution was chargedinto the fore-mentioned autoclave using a syringe. After carrying outthe polymerization for 1 hour, the polymerization was stopped bycharging 5 ml of methanol. After purging out the unreacted propylene,the contents of the autoclave were charged into about 1000 ml of acidicmethanol, and the precipitated polymer was separated by filtration andthen dried for about 2 hours at 80° C. As a result, 1.2 g of apolypropylene was obtained. The [η] of the polypropylene obtained was2.5 dl/g, Mw/Mn was 2.0, mmmm % was 93.8% and melting point was 152.2°C.

EXAMPLE 29

The atmosphere of a 1 liter stainless autoclave was replaced with argon,and propylene was introduced under a pressure of 0.3 MPa after charging300 ml of toluene. Then, after raising a temperature to 40° C., 2.0 mmolof MMAO1 as a molar amount of Al atom and 0.2 mmol of water were chargedtherein under pressurization, and the mixture was mixed by stirring for10 minutes. Further, 0.2 mmol of pentafluorophenol was charged thereinby pressurization, and the mixture was stirred for 10 minutes.

On the other hand, in an egg-plant type flask of an inner volume of 25ml in which the atmosphere was replaced with argon, 5 ml of purifiedtoluene and 0.5 μmol ofdimethylsilylenebis(2-methyl-4-naphthyl-1-indenyl)zirconium dichloridewere mixed by stirring, and then the solution was charged into thefore-mentioned autoclave using a syringe. The polymerization was carriedout for 1 hour. Propylene was continuously fed so that the pressure ofpropylene becomes always 0.3 MPa. Then, the polymerization was stoppedby charging 5 ml of methanol. After purging out the unreacted propylene,the contents of the autoclave were charged into about 1000 ml of acidicmethanol, and the precipitated polymer was separated by filtration andthen dried for about 2 hours at 80° C. As a result, 2.0 g of apolypropylene was obtained. The Mw of the polypropylene obtained was260×10⁴, Mw/Mn was 2.0, mmmm % was 98.6% and melting point was 161.3° C.

COMPARATIVE EXAMPLE 12

The atmosphere of a 1 liter stainless autoclave was replaced with argon,and propylene was introduced under a pressure of 0.3 MPa after charging300 ml of toluene. Then, after raising a temperature to 40° C., 2.0 mmolof MMAO1 as a molar amount of Al atom was charged therein. On the otherhand, in an egg-plant type flask of an inner volume of 25 ml in whichthe atmosphere was replaced with argon, 5 ml of purified toluene and 0.5μmol of dimethylsilylenebis(2-methyl-4-naphthyl-1-indenyl)zirconiumdichloride were mixed by stirring, and then the solution was chargedinto the fore-mentioned autoclave using a syringe. The polymerizationwas carried out for 1 hour. Propylene was continuously fed so that thepressure of propylene-becomes always 0.3 MPa. Then, the polymerizationwas stopped by charging 5 ml of methanol. After purging out theunreacted propylene, the contents of the autoclave were charged intoabout 1000 ml of acidic methanol, and the precipitated polymer wasseparated by filtration and then dried for about 2 hours at 80° C. As aresult, 1.1 g of a polypropylene was obtained. The Mw of thepolypropylene obtained was 219×10⁴, Mw/Mn was 2.5, mmmm % was 98.0% andmelting point was 160.5° C.

According to the present invention, there is provided a modifiedaluminum oxy compound useful as a component of a polymerization catalystcapable of producing a high molecular weight olefin polymer with a highefficiency. Further, there are provided a polymerization catalystobtained by using the modified aluminum oxy compound, and a process forproducing an olefin polymer or an alkenyl aromatic hydrocarbon polymerwith the polymerization catalyst, and a copolymer of an alkenyl aromatichydrocarbon and an olefin.

1. A polymerization catalyst obtained by a process that comprisescontacting (A) a modified aluminum oxy compound obtained by a processthat comprises reacting: an aluminum oxy compound(a) having a ratio ofan intensity at 30 ppm(H2) to an intensity at 10 ppm(H1) [H2/H1] in an²⁷Al-solid NMR spectrum of less than 0.35, water(b), and a compound(c)having a hydroxy group selected from the group consisting of tertiaryalcohols and alcohols substituted with a halogen atom, the alcoholssubstituted with a halogen being selected from the group consisting ofalcohols indicated by the formula CR¹R²R³—OH (wherein each of R¹, R² andR³ independently represents a hydrogen atom or hydrocarbon group having1 to 20 carbon atoms, which is optionally substituted with a halogenatom and they may be mutually the same or different), halogenated phenolcompounds and silanol compounds, wherein the modified aluminum oxycompound (A) has a ratio of an intensity at 30 ppm(M2) to an intensityat 10 ppm(M1)[M2/M1] in an ²⁷Al-solid NMR spectrum of 0.60 or more, themolar ratio[(a)/(b)] of aluminum oxy compound(a) to water(b) is 1/3 to1/0.01, and the molar ratio [(a)/(c)] of the aluminum oxy compound(a) tothe compound(c) is 1/3 to 1/0.01 with (B) a transition metal compound.2. A polymerization catalyst obtained by a process that comprisescontacting (A) a modified aluminum oxy compound obtained by a processthat comprises reacting: an aluminum oxy compound (a) having a ratio ofan intensity at 30 ppm(H2) to an intensity at 10 ppm(H1) [H2/H1] in an²⁷Al-solid NMR spectrum of less than 0.35, water (b), and a compound (c)having a hydroxy group, wherein the modified aluminum oxy compound has aratio of an intensity at 30 ppm(M2) to an intensity at 30 ppm(M1)[M2/M1] in an ²⁷Al-solid NMR spectrum of 0.60 or more, the molar ratio[(a)/(b)] of the aluminum oxy compound (a) to water (b) is 1/3 to1/0.01, and the molar ratio [(a)/(c)] of the aluminum oxy compound (a)to the compound (c) is 1/3 to 1/0.01; with (B) a transition metalcompound.
 3. A polymerization catalyst obtained by a process thatcomprises contacting (A) a modified aluminum oxy compound obtained by aprocess that comprises reacting: an aluminum oxy compound(a′) having aratio of an intensity at 30 ppm(L2) to an intensity at 10 ppm(L1)[L2/L1] in an ²⁷Al-solid NMR spectrum of not less than 0.35, which isobtained by reacting an aluminum oxy compound(a) having a ratio of anintensity at 30 ppm(H2) to an intensity at 10 ppm(H1)[H2/H1] in an²⁷Al-solid NMR spectrum of less than 0.35 and water (b); and acompound(c) having a hydroxy group selected from the group consisting oftertiary alcohols and alcohols substituted with a halogen atom, thealcohols substituted with a halogen being selected from alcoholsindicated by the formula CR¹R²R³—OH (wherein each of R¹, R² and R³independently represents a hydrogen atom or hydrocarbon group having 1to 20 carbon atoms, which is optionally substituted with a halogen atom,and they may be mutually the same or different), halogenated phenolcompounds and silanol compounds, wherein the modified aluminum oxycompound (A) has a ratio of an intensity at 30 ppm(M2) to an intensityat 10 ppm(M1) [M2/M1] in an ²⁷Al-solid NMR spectrum of 0.60 or more, themolar ratio[(a)/(b)] of the aluminum oxy compound(a) to water(b) is 1/3to 1/0.01, and the molar ratio[(a)/(c)] of the aluminum oxy compound(a)to the compound(c) is 1/3 to 1/0.01 and contacting said aluminum oxycompound (A); with (B) a transition metal compound.
 4. A polymerizationcatalyst obtained by a process that comprises contacting (A) a modifiedaluminum oxy compound obtained by a process that comprises reacting: analuminum oxy compound (a′) having a ratio of an intensity at 30 ppm(L2)to an intensity at 10 ppm(L1) [L2/L1] in an ²⁷Al-solid NMR spectrum ofnot less than 0.35, which is obtained by reacting an aluminum oxycompound (a) having a ratio of an intensity at 30 ppm(H2) to anintensity at 10 ppm(H1) [H2/H1] in an ²⁷Al-solid NMR spectrum of lessthan 0.35 and water (b); and a compound (c) having a hydroxy wherein themodified oxy compound (A) has a ratio of an intensity at 30 ppm (M2) toan intensity at 10 ppm (M1) [M2/M1] in an ²⁷Al-solid NMR spectrum of0.60 or more, the molar ratio [(a)/(b)] of the aluminum oxy compound (a)to water (b) is 1/3 to 1/0.01, and the molar ratio [(a)/(c)] of thealuminum oxy compound (a) to the compound (c) is 1/3 to 1/0.01; with (B)a transition metal compound.
 5. A polymerization catalyst obtained by aprocess that comprises contacting (A) a modified aluminum oxy compoundobtained by a process that comprises reacting: an aluminum oxycompound(a″) having a ratio of an intensity at 30 ppm(N2) to anintensity at 10 ppm(N1) [N2/N1] in an ²⁷Al-solid NMR spectrum of notless than 0.35 obtained by reacting an aluminum oxy compound(a) having aratio of an intensity at 30 ppm(H2) to an intensity at 10 ppm H][H2/H1]in its ²⁷Al-solid NMR spectrum of less than 0.35 and a compound(c)having a hydroxy group selected from the group consisting of tertiaryalcohols and alcohols substituted with a halogen atom, the alcoholssubstituted with a halogen being selected from alcohols indicated by theformula CR¹R²R³—OH (wherein each of R¹, R² and R³ independentlyrepresents a hydrogen atom or hydrocarbon group having 1 to 20 carbonatoms, which is optionally substituted with a halogen atom, and they maybe mutually the same or different), halogenated phenol compounds andsilanol compounds, with water(b), wherein the modified aluminum oxycompound (A) has a ratio of an intensity at 30 ppm(M2) to an intensityat 10 ppm(M1)[M2/M1] in an ²⁷Al-solid NMR spectrum of 0.60 or more, themolar ratio[(a)/(b)] of the aluminum oxy compound(a) to water(b) is 1/3to 1/0.01, and the molar ratio[(a)/(c)] of the aluminum oxy compound(a)to the compound(c) is 1/3 to 1/0.01; and contacting (A) with atransition metal compound.
 6. A polymerization catalyst obtained by aprocess that comprises contacting either: (A) the modified aluminum oxycompound of claim 1, (B) a transition metal compound, and (C) anorganoaluminum compound; or (A) the modified aluminum oxy compound ofclaim 1, (B) a transition metal compound, (C) an organoaluminumcompound, and (D) any one of (D1) a boron compound represented by thegeneral formula BQ¹Q²Q³, (D2) a boron compound represented by thegeneral formula G⁺(BQ¹Q²Q³Q⁴)⁻ and (D3) a boron compound represented bythe general formula (L—H)⁺(BQ¹Q²Q³Q⁴)⁻, wherein B represents a boronatom in the trivalent valence state: Q¹ to Q³ may be the same ordifferent and represent a halogen atom, a hydrocarbon group, ahalogenated hydrocarbon group, a substituted silyl group, an alkoxygroup or a di-substituted amino group, G⁺ represents an inorganic ororganic cation; and (L—H)⁺ represents a Brφnsted acid.
 7. Apolymerization catalyst obtained by a process that comprises contactingeither: (A) the modified aluminum oxy compound of claim 2, (B) atransition metal compound, and (C) an organoaluminum compound; or (A)the modified aluminum oxy compound of claim 2, (B) a transition metalcompound, (C) an organoaluminum compound, and (D) any one of (D1) aboron compound represented by the general formula BQ¹Q²Q³, (D2) a boroncompound represented by the general formula G⁺(BQ¹Q²Q³Q⁴)⁻ and (D3) aboron compound represented by the general formula (L—H)⁺(BQ¹Q²Q³Q⁴)⁻,wherein B represents a boron atom in the trivalent valence state; Q¹ toQ³ may be the same or different and represent a halogen atom, ahydrocarbon group, a halogenated hydrocarbon group, a substituted silylgroup, an alkoxy group or a di-substituted amino group; G⁺ represents aninorganic or organic cation: and (L—H)⁺ represents a Brφnsted acid.
 8. Apolymerization catalyst obtained by a process that comprises contactingeither: (A) the modified aluminum oxy compound of claim 3, (B) atransition metal compound, and (C) an organoaluminum compound; or (A)the modified aluminum oxy compound of claim 3, (B) a transition metalcompound, (C) an organoaluminum compound, and (D) any one of (D1) aboron compound represented by the general formula BQ¹Q²Q³, (D2) a boroncompound represented by the general formula G⁺(BQ¹Q²Q³Q⁴)⁻ and (D3) aboron compound represented by the general formula (L—H)⁺(BQ¹Q²Q³Q⁴)⁻,wherein B represents a boron atom in the trivalent valence state; Q¹ toQ³ may be the same or different and represent a halogen atom, ahydrocarbon group, a halogenated hydrocarbon group, a substituted silylgroup, an alkoxy group or a di-substituted amino group; G⁺ represents aninorganic or organic cation; and (L—H)⁺ represents a Brφnsted acid.
 9. Apolymerization catalyst obtained by a process that comprises contactingeither: (A) the modified aluminum oxy compound of claim 4, (B) atransition metal compound, and (C) an organoaluminum compound; or (A)the modified aluminum oxy compound of claim 4, (B) a transition metalcompound, (C) an organoaluminum compound, and (D) anyone of (D1) a boroncompound represented by the general formula BQ¹Q²Q³, (D2) a boroncompound represented by the general formula G⁺(BQ¹Q²Q³Q⁴)⁻ and (D3) aboron compound represented by the general formula (L—H)⁺(BQ¹Q²Q³Q⁴)⁻,wherein B represents a boron atom in the trivalent valence state; Q¹ toQ³ may be the same or different and represent a halogen atom, ahydrocarbon group, a halogenated hydrocarbon group, a substituted silylgroup, an alkoxy group or a di-substituted amino group; G⁺ represents aninorganic or organic cation; and (L—H)⁺ represents a Brφnsted acid. 10.A polymerization catalyst obtained by a process that comprisescontacting either: (A) the modified aluminum oxy compound of claim 5,(B) a transition metal compound, and (C) an organoaluminum compound; or(A) the modified aluminum oxy compound of claim 5, (B) a transitionmetal compound, (C) an organoaluminum compound, and (D) any one of (D1)a boron compound represented by the general formula BQ¹Q²Q³, (D2) aboron compound represented by the general formula G⁺(BQ¹Q²Q³Q⁴)⁻ and(D3) a boron compound represented by the general formula(L—H)⁺(BQ¹Q²Q³Q⁴)⁻, wherein B represents a boron atom in the trivalentvalence state; Q¹ to Q³ may be the same or different and represent ahalogen atom, a hydrocarbon group, a halogenated hydrocarbon group, asubstituted silyl group, an alkoxy group or a di-substituted aminogroup; G⁺ represents an inorganic or organic cation; and (L—H)⁺represents a Brφnsted acid.
 11. A process for producing an olefinpolymer, which comprises homopolymerizing an olefin or copolymerizingolefins with the polymerization catalyst of claim
 1. 12. A process forproducing an olefin polymer, which comprises homopolymerizing an olefinor copolymerizing olefins with the polymerization catalyst of claim 2.13. A process for producing an olefin polymer, which compriseshomopolymerizing an olefin or copolymerizing olefins with thepolymerization catalyst of claim
 3. 14. A process for producing anolefin polymer, which comprises homopolymerizing an olefin orcopolymerizing olefins with the polymerization catalyst of claim
 4. 15.A process for producing an olefin polymer, which compriseshomopolymerizing an olefin or copolymerizing olefins with thepolymerization catalyst of claim
 5. 16. A process for producing anolefin polymer, which comprises homopolymerizing an olefin orcopolymerizing olefins with the polymerization catalyst of claim
 6. 17.A process for producing an olefin polymer, which compriseshomopolymerizing an olefin or copolymerizing olefins with thepolymerization catalyst of claim
 7. 18. A process for producing anolefin polymer, which comprises homopolymerizing an olefin orcopolymerizing olefins with the polymerization catalyst of claim
 8. 19.A process for producing an olefin polymer, which compriseshomopolymerizing an olefin or copolymerizing olefins with thepolymerization catalyst of claim
 9. 20. A process for producing anolefin polymer, which comprises homopolymerizing an olefin orcopolymerizing olefins with the polymerization catalyst of claim
 10. 21.A process for producing an olefin polymer according to claim 11, whereinsaid olefin polymer is a copolymer of ethylene and α-olefin having 3 to20 carbon atoms.
 22. A process for producing an olefin polymer accordingto claim 12, wherein said olefin polymer is a copolymer of ethylene andα-olefin having 3 to 20 carbon atoms.
 23. A process for producing anolefin polymer according to claim 13, wherein said olefin polymer is acopolymer of ethylene and α-olefin having 3 to 20 carbon atoms.
 24. Aprocess for producing an olefin polymer according to claim 14, whereinsaid olefin polymer is a copolymer of ethylene and α-olefin having 3 to20 carbon atoms.
 25. A process for producing an olefin polymer accordingto claim 15, wherein said olefin polymer is a copolymer of ethylene andα-olefin having 3 to 30 carbon atoms.
 26. A process for producing anolefin polymer according to claim 11, wherein said olefin polymer is ahomopolymer of 1-butene.
 27. A process for producing an olefin polymeraccording to claim 12, wherein said olefin polymer is a homopolymer of1-butene.
 28. A process for producing an olefin polymer according toclaim 13, wherein said olefin polymer is a homopolymer of 1-butene. 29.A process for producing an olefin polymer according to claim 14, whereinsaid olefin polymer is a homopolymer of 1-butene.
 30. A process forproducing an olefin polymer according to claim 15, wherein said olefinpolymer is a homopolymer of 1-butene.
 31. A process for producing analkenyl aromatic hydrocarbon polymer, which comprises homopolymerizingan alkenyl aromatic hydrocarbon or copolymerizing at least one alkenylaromatic hydrocarbon and at least one olefin with the polymerizationcatalyst of claim
 1. 32. A process for producing an alkenyl aromatichydrocarbon polymer, which comprises homopolymerizing an alkenylaromatic hydrocarbon or copolymerizing at least one alkenyl aromatichydrocarbon and at least one olefin with the polymerization catalyst ofclaim
 2. 33. A process for producing an alkenyl aromatic hydrocarbonpolymer, which comprises homopolymerizing an alkenyl aromatichydrocarbon or copolymerizing at least one alkenyl aromatic hydrocarbonand at least one olefin with the polymerization catalyst of claim
 3. 34.A process for producing an alkenyl aromatic hydrocarbon polymer, whichcomprises homopolymerizing an alkenyl aromatic hydrocarbon orcopolymerizing at least one alkenyl aromatic hydrocarbon and at leastone olefin with the polymerization catalyst of claim
 4. 35. A processfor producing an alkenyl aromatic hydrocarbon polymer, which compriseshomopolymerizing an alkenyl aromatic hydrocarbon or copolymerizing atleast one alkenyl aromatic hydrocarbon and at least one olefin with thepolymerization catalyst of claim
 5. 36. An α-olefin polymerizationcatalyst according to claim 1, wherein the transition metal compound (B)is a transition metal compound having a capability of stereoregularpolymerization of an α-olefin.
 37. An α-olefin polymerization catalystaccording to claim 2, wherein the transition metal compound (B) is atransition metal compound having a capability of stereoregularpolymerization of an α-olefin.
 38. An α-olefin polymerization catalystaccording to claim 3, wherein the transition metal compound (B) is atransition metal compound having a capability of stereoregularpolymerization of an α-olefin.
 39. An α-olefin polymerization catalystaccording to claim 4, wherein the transition metal compound (B) is atransition metal compound having a capability of stereoregularpolymerization of an α-olefin.
 40. An α-olefin polymerization catalystaccording to claim 5, wherein the transition metal compound (B) is atransition metal compound having a capability of stereoregularpolymerization of an α-olefin.
 41. An α-olefin polymerization catalystaccording to claim 36, wherein the transition metal compound having acapability of stereoregular polymerization of an α-olefin is atransition metal compound (b1) represented by the general formula (4) or(5) below:

(wherein M is a transition metal atom of the Group IV of the PeriodicTable, L¹ is an η⁵-indenyl group or a substituted η⁵-indenyl group, andtwo L¹'s may be mutually the same or different; Y¹ is a carbon atom, asilicon atom, a germanium atom or a tin atom, each of R¹¹ and X¹ is ahydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an arylgroup, a substituted silyl group, an alkoxy group, an aralkyloxy group,an aryloxy group or a heterocyclic group, and all of R¹¹ and X¹ may bethe same or different mutually, P is 1 or 2); or

(wherein M is a transition metal atom of the Group IV of the PeriodicTable, Y² is a silicon atom, a germanium atom or a tin atom, each of(R¹² _(d)—C₅H_(4−n)) and R¹² _(q)—C₅H_(4−q)) is a substitutedη⁵-cyclopentadienyl group, and each of n and q is an integer of 1 to 3;the respective R¹² may be mutually the same or different, and indicate ahalogen atom, an alkyl group, an aralkyl group, an aryl group, asubstituted silyl group, an alkoxy group, an aralkyloxy group, anaryloxy group or a heterocyclic group; the position and/or kind of R¹²in the substituted η⁵-cyclopentadienyl group is selected so that asymmetric plane including M does not exist; each of R¹³ and X² is ahydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an arylgroup, a substituted silyl group, an alkoxy group, an aralkyloxy group,an aryloxy group or a heterocyclic group, and all of R¹³ and X² may bethe same or different mutually).
 42. An α-olefin polymerization catalystaccording to claim 37, wherein the transition metal compound having acapability of stereoregular polymerization of an α-olefin is atransition metal compound (b1) represented by the general formula (4) or(5) below:

(wherein M is a transition metal atom of the Group IV of the PeriodicTable, L¹ is an η⁵-indenyl group or a substituted η⁵-indenyl group, andtwo L¹'s may be mutually the same or different; Y¹ is a carbon atom, asilicon atom, a germanium atom or a tin atom, each of R¹¹ and X¹ is ahydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an arylgroup, a substituted silyl group, an alkoxy group, an aralkyloxy group,an aryloxy group or a heterocyclic group, and all of R¹¹ and X¹ may bethe same or different mutually, P is 1 or 2); or

(wherein M is a transition metal atom of the Group IV of the PeriodicTable, Y² is a silicon atom, a germanium atom or a tin atom, each of(R¹² _(n)—C₅H_(4−n)) and (R¹² _(q)—C₅H_(4−q)) is a substitutedη⁵-cyclopentadienyl group, and each of n and q is an integer of 1 to 3;the respective R¹² may be mutually the same or different, and indicate ahalogen atom, an alkyl group, an aralkyl group, an aryl group, asubstituted silyl group, an alkoxy group, an aralkyloxy group, anaryloxy group or a heterocyclic group; the position and/or kind of R¹²in the substituted η⁵-cyclopentadienyl group is selected so that asymmetric plane including M does not exist; each of R¹³ and X² is ahydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an arylgroup, a substituted silyl group, an alkoxy group, an aralkyloxy group,an aryloxy group or a heterocyclic group, and all of R¹³ and X² may bethe same or different mutually).
 43. An α-olefin polymerization catalystaccording to claim 38, wherein the transition metal compound having acapability of stereoregular polymerization of an α-olefin is atransition metal compound (b1) represented by the general formula (4) or(5) below:

(wherein M is a transition metal atom of the Group IV of the PeriodicTable, L¹ is an η⁵-indenyl group or a substituted η⁵-indenyl group, andtwo L¹'s may be mutually the same or different; Y¹ is a carbon atom, asilicon atom, a germanium atom or a tin atom, each of R¹¹ and X¹ is ahydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an arylgroup, a substituted silyl group, an alkoxy group, an aralkyloxy group,an aryloxy group or a heterocyclic group, and all of R¹¹ and X¹ may bethe same or different mutually, P is 1 or 2); or

(wherein M is a transition metal atom of the Group IV of the PeriodicTable, Y² is a silicon atom, a germanium atom or a tin atom, each of(R¹² _(n)—C₅H_(4−n)) and (R¹² _(q)—C₅H_(4−q)) is a substitutedη⁵-cyclopentadienyl group, and each of n and q is an integer of 1 to 3;the respective R¹² may be mutually the same or different, and indicate ahalogen atom, an alkyl group, an aralkyl group, an aryl group, asubstituted silyl group, an alkoxy group, an aralkyloxy group, anaryloxy group or a heterocyclic group, the position and/or kind of R¹²in the substituted η⁵-cyclopentadienyl group is selected so that asymmetric plane including M does not exist; each of R¹³ and X² is ahydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an arylgroup, a substituted silyl group, an alkoxy group, an aralkyloxy group,an aryloxy group or a heterocyclic group, and all of R¹³ and X² may bethe same or different mutually).
 44. An α-olefin polymerization catalystaccording to claim 39, wherein the transition metal compound having acapability of stereoregular polymerization of an α-olefin is atransition metal compound (b1) represented by the general formula (4) or(5) below:

(wherein M is a transition metal atom of the Group IV of the PeriodicTable, L¹ is an η⁵-indenyl group or a substituted η⁵-indenyl group, andtwo L¹'s may be mutually the same or different; Y¹ is a carbon atom, asilicon atom, a germanium atom or a tin atom, each of R¹¹ and X¹ is ahydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an arylgroup, a substituted silyl group, an alkoxy group, an aralkyloxy group,an aryloxy group or a heterocyclic group, and all of R¹¹ and X¹ may bethe same or different mutually, P is 1 or 2); or

(wherein M is a transition metal atom of the Group IV of the PeriodicTable, Y² is a silicon atom, a germanium atom or a tin atom, each of(R¹² _(n)—C₅H_(4−n)) and (R¹² _(q)—C₅H_(4−q)) is a substitutedη⁵-cyclopentadienyl group, and each of n and q is an integer of 1 to 3,the respective R¹² may be mutually the same or different, and indicate ahalogen atom, an alkyl group, an aralkyl group, an aryl group, asubstituted silyl group, an alkoxy group, an aralkyloxy group, anaryloxy group or a heterocyclic group; the position and/or kind of R¹²in the substituted η⁵-cyclopentadienyl group is selected so that asymmetric plane including M does not exist; each of R¹³ and X² is ahydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an arylgroup, a substituted silyl group, an alkoxy group, an aralkyloxy group,an aryloxy group or a heterocyclic group, and all of R¹³ and X² may bethe same or different mutually).
 45. An α-olefin polymerization catalystaccording to claim 40, wherein the transition metal compound having acapability of stereoregular polymerization of an α-olefin is atransition metal compound (b1) represented by the general formula (4) or(5) below:

(wherein M is a transition metal atom of the Group IV of the PeriodicTable, L¹ is an η⁵-indenyl group or a substituted η⁵-indenyl group, andtwo L¹'s may be mutually the same or different; Y¹ is a carbon atom, asilicon atom, a germanium atom or a tin atom, each of R¹¹ and X¹ is ahydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an arylgroup, a substituted silyl group, an alkoxy group, an aralkyloxy group,an aryloxy group or a heterocyclic group, and all of R¹¹ and X¹ may bethe same or different mutually, P is 1 or 2); or

(wherein M is a transition metal atom of the Group IV of the PeriodicTable, Y² is a silicon atom, a germanium atom or a tin atom, each of(R¹² _(n)—C₅—H_(4−n)) and (R¹² _(q)—C₅H_(4−q)) is a substitutedη⁵-cyclopentadienyl group, and each of n and q is an integer of 1 to 3;the respective R¹² may be mutually the same or different, and indicate ahalogen atom, an alkyl group, an aralkyl group, an aryl group, asubstituted silyl group, an alkoxy group, an aralkyloxy group, anaryloxy group or a heterocyclic group; the position and/or kind of R¹²in the substituted η⁵-cyclopentadienyl group is selected so that asymmetric plane including M does not exist; each of R¹³ and X² is ahydrogen atom, a halogen atom, an alkyl group, an aralkyl group, an arylgroup, a substituted silyl group, an alkoxy group, an aralkyloxy group,an aryloxy group or a heterocyclic group, and all of R¹³ and X² may bethe same or different mutually).
 46. A process for producing an α-olefinpolymer, which comprises polymerizing an α-olefin with the α-olefinpolymerization catalyst of claim
 36. 47. A process for producing anα-olefin polymer, which comprises polymerizing an α-olefin with theα-olefin polymerization catalyst of claim
 37. 48. A process forproducing an α-olefin polymer, which comprises polymerizing an α-olefinwith the α-olefin polymerization catalyst of claim
 38. 49. A process forproducing an α-olefin polymer, which comprises polymerizing an α-olefinwith the α-olefin polymerization catalyst of claim
 39. 50. A process forproducing an α-olefin polymer, which comprises polymerizing an α-olefinwith the α-olefin polymerization catalyst of claim
 40. 51. The processfor producing an α-olefin polymer according to claim 46, wherein theα-olefin polymer is an isotactic propylene polymer.
 52. The process forproducing an α-olefin polymer according to claim 47, wherein theα-olefin polymer is an isotactic propylene polymer.
 53. The process forproducing an α-olefin polymer according to claim 48, wherein theα-olefin polymer is an isotactic propylene polymer.
 54. The process forproducing an α-olefin polymer according to claim 49, wherein theα-olefin polymer is an isotactic propylene polymer.
 55. The process forproducing an α-olefin polymer according to claim 50, wherein theα-olefin polymer is an isotactic propylene polymer.